(19)
(11) EP 0 174 019 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
01.03.1989 Bulletin 1989/09

(21) Application number: 85111166.6

(22) Date of filing: 04.09.1985
(51) International Patent Classification (IPC)4C25D 15/02

(54)

Steel strip plated with a zinc-based coating layer containing an inorganic dispersoid

Stahlband mit einem Dispersionsüberzug auf Zinkbasis und anorganischen Teilchen

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


(84) Designated Contracting States:
DE FR GB IT

(30) Priority: 06.09.1984 JP 185300/84

(43) Date of publication of application:
12.03.1986 Bulletin 1986/11

(73) Proprietor: NIPPON STEEL CORPORATION
Tokyo 100 (JP)

(72) Inventors:
  • Kitayama, Minoru c/o Nippon Steel Corporation
    Sagamihara-shi Kanagawa (JP)
  • Miyoshi, Yasuhiko c/o Nippon Steel Corporation
    Sagamihara-shi Kanagawa (JP)
  • Nishimura, Kazumi c/o Nippon Steel Corporation
    Sagamihara-shi Kanagawa (JP)
  • Shindo, Yoshio c/o Nippon Steel Corporation
    Kimitsu-shi Chiba (JP)
  • Yamazaki, Fumio c/o Nippon Steel Corporation
    Kimitsu-shi Chiba (JP)

(74) Representative: Kador & Partner 
Corneliusstrasse 15
80469 München
80469 München (DE)


(56) References cited: : 
   
  • METAL FINISHING ABSTRACTS, vol. 18, no. 5, September/October 1976, page 254, Hampton Hill, GB; & JP - A - 51 5242 (NIPPON STEEL CORP.) 03-07-1974
  • METAL FINISHING ABSTRACTS, vol. 22, no. 4, July/August 1980, page 263, Hampton Hill, GB; & JP - A - 54 146 228 (NIPPON STEEL CORP.) 08-05-1978
  • CHEMICAL ABSTRACTS, vol. 92, 1980, page 818, no. 206075m, Columbus, Ohio, US; & JP - A - 79 159 342 (NIPPON STEEL CORP.)17-12-1979
  • CHEMICAL ABSTRACTS, vol. 92, 1980, page 573, no. 84924q, Columbus, Ohio, US; & JP - A - 79 146 228 (NIPPON STEEL CORP.) 15-11-1979
  • METAL FINISHING ABSTRACTS, vol. 22, no. 6, November/December 1980, page 292, Hampton Hill, GB; O.G. POPOV et al.: "Production of two-layer zinc-chromium coatings on steel and investigation of their protective power", & R.ZH. KORR. I ZASHCH. OT. KORR. 1980, 4K336
   
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Background of the invention


(1) Field of the invention



[0001] 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.

(2) Description of the related art



[0002] Generally, 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.

[0003] Also, surface-treated steel strips must exhibit excellent workability and weldability.

[0004] In response to the above-mentioned requirements, various types of plated steel strips having zinc-based coating layers are used, and there have been various attempts to improve plated steel strips having zinc-based coating layers.

[0005] Japanese Examined Patent Publication No. 56-49999 discloses a plated steel strip having an electroplating layer comprising a matrix consisting of zinc alone and 2.0 to 15% of Si02 particles, and optionally, an electroplating surface layer consisting of 1 g/m2 or more of zinc alone.

[0006] Japanese Examined Patent Publication No. 57-17960 discloses a plated steel strip having a base plating layer consisting of zinc alone and a surface plating layer comprising a matrix consisting of Mn alone and particles consisting of at lesat one member selected from metallic Ni, Cu, AI and Cr and oxides of Ti, AI and Mg, and having a thickness of 0.1 µm or more.

[0007] Japanese Examined Patent Publication No. 46-37882 discloses a plated light metal article having a base plating layer consisting of zinc alone and a surface electroplating layer comprising a matrix consisting of nickel alone and a dispersoid consisting of solid particles having a size of 1 1l[11 or less and located in the surface portion of the surface electroplating layer.

[0008] Japanese Unexamined Patent Publication No. 56-123,395 discloses a plated steel strip having an electroplating layer comprising a matrix consisting of zinc alone or a Ni-Zn alloy and chromium hydrate particles having a size of 0.3 pm or more and dispersed in the surface portion of the layer with a depth of 0.3 pm from the surface of the layer.

[0009] Japanese Unexamined Patent Publication No. 52-109,439 discloses a plated metal article having a base electroplating layer consisting of nickel alone and a surface electroplating layer comprising a nickel matrix and silicon carbide particles. However, the resultant plated steel strips are not always satisfactory in view of the strict requirements mentioned above.

[0010] Under the above-mentioned circumstances, it is strongly desired to provide a new type of plated steel strip which exhibits excellent resistance to corrosion after painting and high resistances to perforation corrosion and powdering after processing.

[0011] JP-A-79 159 342 discloses a process for producing a corrosion resistant plated composite steel strip in which a surface of a steel strip substrate is coated with an electroplating layer comprising a matrix consisting of zinc and fine particles consisting of Si02 sol, Ti02 sol and Zr02 sol, and dispersed in the zinc matrix.

[0012] JP-A-79 146 228 discloses a plated steel strip in which a cold-rolled steel strip substrate is coated with an electroplating base layer consisting of a matrix consisting of zinc alone and Si02 fine particles, and the base layer is coated with an electroplating surface layer consisting of zinc alone.

[0013] Metal Finishing Abstracts, vol. 22, No. 6, November/December 1980, page 292 discloses a plated steel strip comprising a steel strip substrate, an under-coating layer composed of a matrix consisting of zinc alone and AI203 particles dispersed in the matrix, and an upper coating layer consisting of chromium alone.

Summary of the invention



[0014] 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.

[0015] Another object of the present invention is to provide a zinc-plated steel strip which exhibits excellent workability and weldability.

[0016] The above-mentioned objects can be attained by 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 zinc alloy 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.

[0017] The zinc-plated steel strip of the present invention may further comprise 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.

Description of the preferred embodiments



[0018] It was found that a 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 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 a 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.

[0019] Furthermore, it was found by the inventors of the present invention that 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.

[0020] 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.

[0021] 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.

[0022] In the zinc-plated steel strip of the present invention, 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 (AI), iron (Fe), titanium (Ti), molybdenum (Mo), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), lanthanum (La), cerium (Ce), and silicon (Si).

[0023] 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, AI-killed steel strips and high tensile steel strips.

[0024] As stated above, when the above-mentioned specific inorganic dispersoid particles are contained in the zinc alloy matrix, 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.

[0025] In the zinc-plated steel strips of the present invention, it is preferable that the surface coating layer be in an amount of from 1 to 400 g/m2, and has a thickness of from 0.1 to 40 pm.

[0026] In the surface coating layer, the matrix consists of 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.

[0027] In the zinc alloy, 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.

[0028] In the surface coating layer, 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.

[0029] When the amount of the inorganic dispersoid in the surface coating layer is less than 0.01 %, the resultant plated steel strip exhibits unsatisfactory weldability.

[0030] When the plated steel strip is required to exhibit extremely high resistance to corrosion, in view of the sacrifice corrosion control effect of the zinc alloy, it is preferable that 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.

[0031] 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 Ilm. Fine inorganic dispersoid particles having an average size of 51lm or less are highly 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.

[0032] 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.

[0033] In the zinc-plated steel strip of the present invention, an intermediate coating layer consisting of zinc or a zinc alloy may be formed between the steel strip substrate and the surface coating layer.

[0034] 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. Preferably, 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.

[0035] The intermediate coating layer is preferably in an amount of from 0.5 to 400 g/m2, more preferably, from 1 to 200 g/m2, and preferably has a thickness of from 0.1 to 20 pm.

[0036] 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.

[0037] The term "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. The term "chemical conversion treatment" refers to a phosphate treatment or a chromate treatment applied to the surface coating layer of the plated steel strip.

[0038] 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.

[0039] 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. Preferably, the electric plating method is applied to the production of the surface coating layer. For example, the electric plating procedure is carried out in a plating bath containing sulfate or chloride of zinc and at least one additional metal having a pH of 1 to 3 at a current density of 1 to 200 A/dm2 at a line speed of 1 to 250 m/min.

[0040] In the production of the surface coating layer, it is not completely clear how 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.

[0041] The intermediate coating layer can be produced by means of electric plating, vacuum evaporation plating, or hot galvanizing.

[0042] 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.

[0043] When one surface of the substrate has a surface coating layer or a combination of an intermediate coating layer and a surface coating layer, 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.

[0044] The present invention will be further explained by way of specific examples, which, however, are representative and do not restrict the scope of the present invention in any way.

[0045] In the examples, the resistance of a specimen to corrosion was determined as follows.

[0046] 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 pm.

[0047] 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.

[0048] 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.

[0049] The resistance of the deep drawn specimen to powdering was determined by a tape test.

[0050] 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.

[0051] The surface rusting test was carried out by a cross-cut method.

[0052] 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:












Examples 1 to 33



[0053] In each of Examples 1 to 33, a surface of a substrate consisting of an ordinary steel strip was plated with a surface coating layer as shown in detail in Table 1(1), (2), and (3). The properties of the resultant plated steel strips are also shown in Table 1(1), (2), and (3).

[0054] In view of Examples 18 to 24, it is preferable that 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.

[0055] In view of Examples 17 to 21, it is preferable for the purpose of enhancing the powdering resistance of the plated steel strip to control the content of the inorganic dispersoid particle to a level not exceeding 30% based on the entire weight of the surface coating layer.

[0056] Tn view of Examples 17 to 23, it is preferable for the purpose of improving the perforation corrosion resistance of the processed portion of the plated steel strip to control the content of the inorganic dispersoid particles to a level not exceeding 95% based on the entire weight of the surface coating layer.

[0057] In view of Examples 25 to 33, 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.

Examples 34 to 164 and Comparative Example 1 to 9



[0058] In each of Examples 34 to 164, except for Examples 116, 118, and 120 to 140, a surface of a substrate consisting of an ordinary steel strip was plated with an intermediate coating layer having the composition and thickness as shown in Table 2 (1) to (9) and then with a surface coating layer having the composition and thickness shown in Table 2.

[0059] In each of Examples 116, 118, and 120 to 140, the same substrate as that mentioned above was directly plated with a surface coating layer having the composition and thickness as indicated in Table 2.

[0060] In 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).

[0061] In Comparative Examples 7 to 9, the same substrate as that mentioned above was plated directly with the surface coating layer as shown in Table 2(9).

[0062] In Example 116, a surface of the substrate was covered partially with the intermediate coating layer at a covering rate of 50%.

[0063] In each of Examples 118 and 119, the surface of the surface coating layer was treated with a silane-coupling agent.

[0064] In Comparative Example 1, wherein the intermediate coating layer contains Si02 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.

[0065] In Comparative Example 2, dispersoid particles consisting of Cr203 resulted in a poor weldability of the resultant plated steel strip.

[0066] In Comparative Examples 3 and 4, a surface coating layer matrix consisting of nickel or manganese resulted in a poor perforation corrosion resistance of the resultant plated steel strip.

[0067] In each of Comparative Examples 5 and 6, the surface coating layer contained no inorganic dispersoid. This feature resulted in poor weldability of the resultant plated steel strip.

[0068] In each of Comparative Examples 7 and 9 the dispersoid consisting of Zr02 or Cr203 resulted in poor powdering resistance and weldability of the resultant plated steel strip.

[0069] In Comparative Example 8, the dispersoid consisting of WC resulted in a poor paint adhesion and in poor weldability of the resultant plated steel strip.

[0070] In view of Examples 120 to 129, the preferable dispersoids for the zinc-nickel alloy matrix in the surface coating layer are oxides of aluminum, iron, titanium, and silicon.

[0071] In view of Examples 130 and 136, the preferable metals to be alloyed with zinc in the surface coating layer are nickel, cobalt, chromium, iron, and manganese.

[0072] In view of Examples 58 to 69, and 92 to 97, 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 Si02 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.

[0073] In view of Examples 98 to 104, the preferable thickness of the surface coating layer is in the range of from 0.1 to 40 microns. Also, in view of Examples 141 to 145, it is preferable that the thickness of the intermediate coating layer is in the range of from 0.1 to 20 microns.

[0074] In view of Examples 107 to 115, it is known that in the surface coating layer matrix consisting of a zinc alloy, when the content of the additional metal to be alloyed with zinc is 0.3% by weight or more, the resultant plated steel strip exhibited an enhanced paint adhesion of a scratched portion. When the content of the additional metal is 80% by weight or less, the processed portion of the plated steel strip exhibited an excellent perforation corrosion resistance.

[0075] Examples 116 and 117 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.

[0076] When the plated steel stripes of the present invention were surface treated with a silane coupling agent, the resultant products exhibited excellent corrosion resistance, workability, and weldability as shown in Examples 118 and 119.






























Claims

1. A zinc-plated steel strip with a zinc-based-coating layer, comprising:

a substrate consisting of a steel strip; and

at least one surface coating layer plated on at least a 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 zinc alloy 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.


 
2. The zinc-plated steel strip as claimed in claim 1, wherein the zinc alloy is selected from alloys of zinc with at least one additional metal member selected from the group consisting of nickel, copper, cobalt, chromium, tellurium, lanthanum, cerium, iron, and manganese.
 
3. The zinc-plated steel strip as claimed in claim 1, which 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.
 
4. The zinc-plated steel strip as claimed in claim 3, wherein the surface coating layer covers partially the surface of the steel strip substrate.
 
5. The zinc-plated steel strip as claimed in claim 3, wherein the intermediate coating layer partially covers the surface of the steel strip substrate.
 
6. The zinc-plated steel strip as claimed in claim 1, wherein the fine dispersoid particles are in an amount of at least 0.01% based on the entire weight of the surface coating layer.
 
7. The zinc-plated steel strip as claimed in claim 1, wherein the fine dispersoid particles are in an amount of from 0.01% to 95% based on the entire weight of the surface coating layer.
 
8. The zinc-plated steel strip as claimed in claim 7, wherein the fine dispersoid particles are in an amount of from 0.01 % to 30% based on the entire weight of the surface coating layer.
 
9. The zinc-plated steel strip as claimed in claim 1 or 3, which further comprises a covering layer formed on the surface coating layer by means of a silane-coupling treatment or a chemical conversion treatment.
 
10. The zinc-plated steel strip as claimed in claim 8, wherein the fine dispersoid particles consisting of at least one member selected from oxides, carbides, nitrides, borides, phosphides, and sulfides of aluminum, iron, titanium, and silicon are dispersed in an amount of 0.01% to 30% based on the entire weight of the surface coating layer in a matrix consisting of a zinc alloy of 99.7% by weight or less of zinc with 0.3% by weight or more of at least one additional member selected from the group consisting of nickel, cobalt, chromium, iron, and manganese.
 
11. The zinc-plated steel strip as claimed in claim 10, wherein the amount of the additional metal member selected from nickel, cobalt, chromium, iron, and manganese is in the range of from 0.3% to 80% by weight.
 
12. The zinc-plated steel strip as claimed in claim 8, wherein the fine dispersoid particles consist of at least one member selected from the group consisting of oxides, carbides, nitrides, borides, phosphides, and sulfides and have an average size of 5 Ilm or less.
 
13. The zinc-plated steel strip as claimed in claim 1, wherein the surface coating layer consist essentially of 0.01 % to 30% by weight of the fine dispersoid particles consisting of at least one member selected from the group consisting of oxides, carbides, nitrides, borides, phosphides and sulfides of aluminum, iron titanium and silicon and having an average size of 5 microns or less and the balance of the matrix consisting of a zinc alloy consisting of 0.5% to 80% by weight of at least one member selected from the group consisting of nickel, cobalt, chromium, iron and manganese at the balance of zinc.
 
14. The zinc-plated steel strip as claimed in claim 13, wherein the surface coating layer is formed on an intermediate coating layer consisting of at least one member selected from the group consisting of zinc and zinc alloys.
 
15. The zinc-plated steel strip as claimed in claim 3, wherein the surface coating layer has a thickness of from 0.1 to 40 pm and comprises 70% to 99.99% by weight of a matrix consisting of a zinc alloy of 20% to 99.7% by weight of zinc with 0.3% to 80% by weight of at least one additional metal member selected form nickel, cobalt, chromium, iron, and manganese, and 0.01% to 30% by weight of fine dispersoid particles consisting of silicon oxide and having an average size of 0.020 µm or less; and the intermediate coating layer has a thickness of from 0.1 to 20 pm and comprises zinc or zinc alloy.
 


Ansprüche

1. Mit Zink plattiertes Stahlband mit einer auf Zink basierenden Überzugsschicht, welches umfaßt:

Ein aus einem Stahlband bestehendes Substrat und

zumindest eine Oberflächenüberzugsschicht, die auf zumindest einen Abschnitt von zumindest einer Oberfläche dieses Stahlbandsubstrats plattiert ist,

wobei die Oberflächenüberzugsschicht im wesentlichen aus einer Matrix besteht, die aus zumindest einer Zinklegierung und feinen Dispersoidpartikeln besteht, die in diese Matrix dispergiert sind und aus zumindest einer Verbindung besteht, die aus der Gruppe ausgewählt ist, die aus Oxiden, Karbiden, Nitriden, Boriden, Phosphiden und Sulfiden von Aluminium, Eisen, Titan, Molybdän, Kupfer, Zink, Nickel, Kobalt, Lanthan, Cer und Silicium besteht.


 
2. Mit Zink plattiertes Stahlband nach Anspruch 1, worin die Zinklegierung aus Legierungen von Zink mit zumindest einer zusätzlichen Metallverbindung ausgewählt ist, die aus der Gruppe ausgewählt ist, die aus Nickel, Kupfer, Kobalt, Chrom, Tellur, Lanthan, Cer, Eisen und Mangan besteht.
 
3. Mit Zink plattiertes Stahlband nach Anspruch 1, das zusätzlich eine Zwischenüberzugsschicht umfaßt, die zwischen dem Stahlbandsubstrat und der Oberflächenüberzugsschicht ausgebildet ist und aus zumindest einer Verbindung besteht, die aus der Gruppe ausgewählt ist, die aus Zink und Zinklegierungen besteht. i
 
4. Mit Zink plattiertes Stahlband nach Anspruch 3, worin die Oberflächenüberzugsschicht teilweise die Oberfläche des Stahlbandsubstrats bedeckt.
 
5. Mit Zink plattiertes Stahlband nach Anspruch 3, worin die Zwischenüberzugsschicht die Oberfläche des Stahlbandsubstrats teilweise bedeckt.
 
6. Mit Zink plattiertes Stahlband nach Anspruch 1, worin die feinen Dispersoidpartikel, bezogen auf das Gesamtgewicht der Oberflächenüberzugsschicht, in einer Menge von mindestens 0,01% vorhanden sind.
 
7. Mit Zink plattiertes Stahlband nach Anspruch 1, worin die feinen Dispersoidpartikel, bezogen auf das Gesamtgewicht der Oberflächenüberzugsschicht, in einer Menge von 0,01 bis 95% vorhanden sind.
 
8. Mit Zink plattiertes Stahlband nach Anspruch 7, worin die feinen Dispersoidpartikel, bezogen auf das Gesamtgewicht der Oberflächenüberzugsschicht, in einer Menge von 0,01 bis 30% vorhanden sind.
 
9. Mit Zink plattiertes Stahlband nach Anspruch 1 oder 3, welches darüberhinaus eine Abdeckschicht umfaßt, die mittels einer Silankopplungsbehandlung oder einer chemischen Umwandlungsbehandlung auf der Oberflächenüberzugsschicht gebildet wurde.
 
10. Mit Zink plattiertes Stahlband nach Anspruch 8, worin die feinen Dispersoidpartikel aus zumindest einer Verbindung bestehen, die aus Oxiden, Karbiden, Nitriden, Boriden, Phosphiden und Sulfiden von Aluminium, Eisen, Titan und Silicium ausgewählt ist und in einer Menge von 0,01 bis 30%, bezogen auf das Gesamtgewicht der Oberflächenüberzugsschicht in eine Matrix dispergiert sind, die aus einer Zinklegierung von 99,7 Gew% oder weniger Zink mit 0,3 Gew% oder mehr von zumindest einer zusätzlichen Verbindung besteht, die aus der Gruppe ausgewählt ist, die aus Nickel, Kobalt, Chrom, Eisen und Mangan besteht.
 
11. Mit Zink plattiertes Stahlband nach Anspruch 10, worin die Menge der zusätzlichen Metallverbindung, die aus Nickel, Kobalt, Chrom, Eisen und Mangan ausgewählt ist, im Bereich von 0,3 bis 80 Gew% liegt.
 
12. Mit Zink plattiertes Stahlband nach Anspruch 8, worin die feinen Dispersoid partikel aus zumindest einer Verbindung bestehen, die aus der Gruppe ausgewählt ist, die aus Oxiden, Karbiden, Nitriden, Boriden, Phosphiden und Sulfiden besteht und eine durchschnittliche Größe von 5 um oder weniger aufweisen.
 
13. Mit Zink plattiertes Stahlband nach Anspruch 1, worin die Oberflächenüberzugsschicht im wesentlichen aus 0,01 bis 30 Gew% feiner Dispersoidpartikel besteht, die aus zumindest einer Verbindung bestehen, die aus der Gruppe ausgewählt ist, die aus Oxiden, Karbiden, Nitriden, Boriden, Phosphiden und Sulfiden von Aluminium, Eisen, Titan und Silicium besteht, und eine durchschnittliche Größe von 5 um oder weniger aufweisen, wobei der Rest der Matrix aus einer Zinklegierung besteht, die aus 0,5 bis 80 Gew% von zumindest einer Verbindung besteht, die aus der Gruppe ausgewählt ist, die aus Nickel, Kobalt, Chrom, Eisen und Mangan besteht, wobei der Rest Zink ist.
 
14. Mit Zink plattiertes Stahlband nach Anspruch 13, worin die Oberflächenüberzugsschicht auf der Zwischenüberzugsschicht ausgebildet ist, die aus zumindest einer Verbindung besteht, die aus der Gruppe ausgewählt ist, die aus Zink und Zinklegierungen besteht.
 
15. Mit Zink plattiertes Stahlband nach Anspruch 3, worin die Oberflächenüberzugsschicht eine Dicke von 0,1 bis 40 µm aufweist und 70 bis 99,99 Gew% einer Matrix umfaßt, die aus einer Zinklegierung von 20 bis 99,7 Gew% Zink, mit 0,3 bis 80 Gew% von zumindest einer zusätzlichen Metallverbindung besteht, die aus Nickel, Kobalt, Chrom, Eisen und Mangan ausgewählt ist, und 0,01 bis 30 Gew% der feinen Dispersoid partikel aus Siliciumoxid bestehen und eine Durchschnittsgröße von 0,020 um oder weniger aufweisen und die Zwischenüberzugsschicht eine Dicke von 0,1 bis 20 um aufweist und Zink oder eine Zinklegierung umfaßt.
 


Revendications

1. Feuillard d'acier revêtu de zinc avec une couche de revêtement à base de zinc comprenant: .

un substrat consistant en un feuillard d'acier; et

au moins une couche de revêtement de surface déposée sur une partie d'au moins une surface du substrat de feuillard d'acier,

la couche de revêtement de surface consistant essentiellement en une matrice consistant en au moins un alliage de zinc et en particules de dispersoïde fines dispersées dans la matrice et consistant en au moins un membre choisi dans le groupe constitué par les oxydes, carbures, nitrures, borures, phosphures et sulfures, d'aluminium, de fer, de titane, de molybdène, de cuivre, de zinc, de nickel, de cobalt, le lanthane, de cérium et de silicium.


 
2. Feuillard d'acier revêtu de zinc selon la revendication 1, dans lequel l'alliage de zinc est choisi entre les alliages de zinc avec au moins un élément métallique additionnel choisi dans le groupe constitué par le nickel, le cuivre, le cobalt, le chrome, le tellure, le lanthane, le cérium, le fer et le manganèse.
 
3. Feuillard d'acier revêtu de zinc selon la revendication 1, qui comprend en outre une couche de revêtement intermédiaire formée entre le substrat de feuillard d'acier et la couche de revêtement de surface et consistant en au moins un membre choisi dans le groupe constitué par le zinc et les alliages de zinc.
 
4. Feuillard d'acier revêtu de zinc selon la revendication 3, dans lequel la couche de revêtement de surface recouvre partiellement la surface du substrat de feuillard d'acier.
 
5. Feuillard d'acier revêtu de zinc selon la revendication 3, dans lequel la couche de revêtement intermédiaire recouvre partiellement la surface du substrat de feuillard d'acier.
 
6. Feuillard d'acier revêtu de zinc selon la revendication 1, dans lequel la quantité des particules de dispersoîde fines est d'au moins 0,01 % par rapport au poids total de la couche de revêtement de surface.
 
7. Feuillard d'acier revêtu de zinc selon la revendication 1, dans lequel la quantité des particules de dispersoïde fines est comprise entre 0,01 % et 95% par rapport au poids total de la couche de revêtement de surface.
 
8. Feuillard d'acier revêtu de zinc selon la revendication 7, dans lequel la quantité des particules de dispersoïde fines est comprise entre 0,01 % et 30% par rapport au poids total de la couche de revêtement de surface.
 
9. Feuillard d'acier revêtu de zinc selon la revendication 1 ou la revendication 3, qui comprend en outre une couche de recouvrement formée sur la couche de revêtement de surface au moyen d'un traitement de couplage au silane ou d'un traitement de transformation chimique.
 
10. Feuillard d'acier revêtu de zinc selon la revendication 8, dans lequel les particules de dispersoïde fines consistant en au moins un membre choisi entre les oxydes, carbures, nitrures, borures, phosphures et sulfures d'aluminium, de fer, de titane et de silicium sont dispersées en une quantité de 0,01 % à 30% sur la base du poids total de la couche du revêtement de surface dans une matrice consistant en un alliage de zinc de 99,7% en poids ou moins de zinc avec 0,3% en poids ou plus d'au moins un membre additionnel choisi dans le groupe constitué par le nickel, le cobalt, le chrome, le fer, et le manganèse.
 
11. Feuillard d'acier revêtu de zinc selon la revendication 10, dans lequel la quantité de l'élément métallique additionnel choisi entre le nickel, le cobalt, le chrome, le fer et le manganèse est comprise entre 0,3% et 80%.
 
12. Feuillard d'acier revêtu de zinc selon la revendication 8, dans lequel les particules de dispersoïde fines consistent en au moins un élément choisi dans le groupe constitué par les oxydes, carbures, nitrures, borures, phosphures et sulfures et ont une taille moyenne de 5 um ou moins.
 
13. Feuillard d'acier revêtu de zinc selon la revendication 1, dans lequel la couche de revêtement de surface consiste essentiellement en 0,01 % à 30% en poids de particules de dispersoïde fines consistant en au moins un élément choisi dans le groupe constitué par les oxydes, carbures, nitrures borures, phosphures et sulfures, d'aluminium, de fer, de titane et de silicium et ayant une taille moyenne de 5 microns ou moins, le reste de la matrice étant constitué d'un alliage de zinc comprenant de 0,5% à 80% en poids d'au moins un élément choisi dans le groupe constitué par le nickel, le cobalt, le chrome, le fer et le manganèse, le reste étant constitué de zinc.
 
14. Feuillard d'acier revêtu de zinc selon la revendication 13, dans lequel la couche de revêtement de surface est formée sur une couche de revêtement intermédiaire consistant en au moins un membre choisi dans le groupe constitué par le zinc et les alliages de zinc.
 
15. Feuillard d'acier revêtu de zinc selon la revendication 3, dans lequel la couche de revêtement de surface a une épaisseur allant de 0,1 à 40 pm et comprend de 70% à 99,99% en poids d'une matrice consistant en un alliage de zinc de 20% à 99,7% en poids de zinc avec de 0,3% à 80% en poids d'au moins un élément métallique additionnel choisi entre le nickel, le cobalt, le chrome, le fer, et le manganèse, et de 0,01 % à 30% en poids de particules de dispersoïde fines constituées d'oxyde de silicium et ayant une taille moyenne de 0,020 Ilm ou moins; et la couche de revêtement intermédiaire a une épaisseur allant de 0,1 à 20 Ilm et comprend du zinc ou un alliage de zinc.