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(11) | EP 0 048 270 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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| (54) |
ZINC-ALUMINUM COATINGS ZINK-ALUMINIUM-BESCHICHTUNGEN REVETEMENTS DE ZINC-ALUMINIUM |
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| 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). |
Technical Field
[0001] The present invention is directed to the application of zinc coatings to a substrate - commonly sheet steel.
[0002] The use of zinc as a protective coating has been known for many years. In this regard, hot dip galvanizing, either continuous or batch type, has long been used for a variety of steel products to protect the products from corrosion.
Background Art
[0003] In order to obtain increased corrosion protection as well as other advantages (e.g. better sacrificial protection of steel; improved formability, weldability and paintability) efforts have been undertaken in the field of zinc coatings to develop improved zinc alloys for the continuous or batch application to substrates. Studies carried out in this direction have resulted in the development of new types of coatings such as the alloy Zn-55 Al-1.5Si and other zinc alloys having low (i.e., less than 15%) AI-1.5Si content. The Zn-55 AI alloy coating developed by Bethlehem Steel (see for example U.S. Patent Nos. 3,343,930 and 3,393,089) reportedly exhibits a good corrosion resistance but, in view of its high aluminum content does not provide a satisfactory sacrificial protection of the steel substrate.
[0004] Subsequent studies have been aimed at modifying the composition of molten metal baths in order to form (by hot-dipping) a coating which improves corrosion resistance even in the most varied environments. One of the aspects of these studies was the influence of the preparation of the surface to be coated on the quality of the product obtained. It thus appears that in order to ensure a quality coating, some alloy coatings previously developed required expensive preliminary sur- face treatments involving expensive equipment, for example, this was the case with respect to zinc coatings containing typically about 5% AI and additions of other elements such as Sb, Pb + Mg, and Pb + Mg + Cu proposed by Inland Steel (see for example Inland U.S. Patent Nos. 4,029,478 and 4,056,366 as well as U.S. Patent No. 4,152, 472 assigned by Nippon Steel). There exists evidence showing that compositions of these types are characterized by a pronounced tendency to form bare-spots and similar defects even in the presence of careful surface preparation.
[0005] In view of the above considerations, there continues a need for a hot-dip metal bath of such composition that no special or expensive surface preparation of the substrate would be necessary and such that the protective coating obtained thereby is substantially free of bare spots. or other defects.
Disclosure of the Invention
[0006] Consistent with the above, there have been developed according to the present invention zinc-containing hot-dip metal baths which yield high quality protective coatings free of defects such as bare spots.
[0007] The invention concerns a protective metal coating, which may be deposited from hot-dip metal bath on a substrate, said coating comprising at least about 85% by weight Zn, from about 3% to about 15% by weight AI and from about 5 ppm to about 1.0% by weight of mischmetal, the percentage of mischmetal being calculated on the total of Zn and Al.
Detailed Description
[0008] The protective metal coating may be obtained by deposition from hot-dip metal baths, and hence the coatings obtained therefrom, may vary considerably just as known zinc-aluminum coatings may vary. In each instance however, it is essential that the coating contains a mischmetal alloy in an amount sufficient to yield the improved results observed and described herein. A mischmetal addition to a zinc-aluminum bath in the range of from about 5 ppm to about 1.0%, and preferably about 0.01% to about 0.1% (by weight), is generally contemplated as being sufficient in this regard.
[0009] As will be understood by one skilled in the art, the term mischmetal refers to a variety of known rare earth alloys. For example, a typical cerium mischmetal might have the following composition (in weight %):
Ce 45-60; other rare earths 35-50, the bal- ahce comprising Fe, Mg, Al, Si and impurities.
[0010] Thus the term mischmetal, as used herein, referes to the above composition as well as other mischmetal compositions readily apparent to those skilled in the art.
[0011] As stated above, the alloy to which mischmetal is to be added is a zinc-aluminum alloy containing from about 3% to about 15% by weight aluminum. Such alloys typically contain about 5% aluminum. These alloys may contain constituents in addition to mischmetal such as Fe, Fb, Sb, Mg, Sn, Cu and Si.
[0012] Thus one embodiment of the invention uses a low aluminum (i.e., 3-15% by weight) zinc bath containing Pb or Sn as well as mischmetal. Pb and Sn are known additives to galvanizing baths for modifying the fluidity of the liquid metal or the spangle of the solidified coating.
[0013] The addition of Sb to a galvanizing bath is disclosed in U.S. Patent No. 4,056,366 to improve the coatability of Zn-AI coatings in a manner similar to lead but without the deleterious effect that lead has upon the intergranular corrosion of the coatings. The addition of Sb to the mischmetal-containing compositions used in the present invention is therefore contemplated. Moreover, the use of a Zn-AI composition containing Pb together with Sb is within the scope of the invention. A typical composition might contain 3-15% by weight Al, 0.03-0.15% by weight Sb, less than 0.02% by weight Pb, and the balance Zn to which mischmetal has been added.
[0014] Zinc-aluminum alloys containing lead and also Mg and Cu are reported to be immune to grain boundary corrosion. In this type of coating alloys, mischmetal additions have been shown to exhibit a pronounced beneficial effect as regards soundness and uniformity. Thus a Zn-AI alloy containing Mg, Pb, Cu and mischmetal is encompassed by the present invention. Here a typical composition might contain 3-15% by weight AI, 0.02-0.15% by weight Mg, 0.02-0.15% by weight Pb and possibly 0.1-0.3% by weight Cu, the balance being Zn with mischmetal additions.
[0015] Various mischmetals may be advantageously used according to the invention, including mixtures of mischmetals in a single zinc bath or coating. For example, a La-mischmetal and a Ce-mischmetal may be added simultaneously, preferably in an amount such that the total mischmetal concentration is within the ranges described above, i.e. from about 5 ppm to about 1.0% and preferably from about 0.01 to 0.1% by weight.
[0016] In order to facilitate the addition of the mischmetal to the galvanizing bath, a master alloy may be first prepared and then added to the zinc bath so as to yield the desired mischmetal concentration. Such master alloys might be comprised of 20% by weight Zn and 80% by weight mischmetal or 85-95% by weight AI and 15-5% by weight mischmetal.
Examples
[0017] 1. Specimens of rimming steel sheet measuring 68 x 120 x 0.7 mm were galvanized in a device simulating a continuous galvanizing bath. They were first preheated in an atmosphere containing 95% NZ 5% H2 at different temperatures from 750 to 800°C for times ranging from 1 to 10 minutes. After this heating stage the specimens. were transferred from the hot zone of the furnace, cooled down to about 430°C and then introduced into a zinc alloy bath maintained at 430°C and protected by the 95% NZ-5% H2 atmosphere. They were maintained in the zinc bath for periods ranging from 5 to 60 seconds and then removed from the bath and cooled in a jet of 95% NZ-5% H2 atmosphere. They were maintained in the zinc bath for periods ranging from 5 to 60 seconds and then removed from the bath and cooled in a jet of 95% N2-5% H2 gas.
[0018] Such tests were carried out with different types of bath compositions. The galvanized samples were examined to determine the soundness of the coating, particularly as regards the occurrence of bare spots and uncoated areas.
[0019] In a bath containing 5 to 8% by weight Al without any other additions, the specimens contained a high proportion of uncoated areas and bare spots. This was the case even as to the specimens pretreated at the highest temperature and longest annealing time in the reducing atmosphere. The addition of 0.15% by weight Sb in a Zn-5% by weight AI bath resulted in a decrease in the amount of bare spots but still. up to 33% of the galvanized faces presented bare spots.
[0020] A third bath containing 5% by weight AI and 0.02% by weight Ce added as Ce-mischmetal resulted in 100% good coatings for a range of heat treating conditions.
[0021] A bath containing Zn-5% by weight Al, 0.03% by weight La and 0.025% by weight Ce added as La and Ce mischmetal gave rise to 100% good coatings even for preheating temperatures as low as 750°C.
[0022] 2. This example relates to trials carried out with a pilot continuous annealing and galvanizing plant. In these trials 800 kg coils of rimming steel sheet 150 mm wide and 0.25 mm thick were first treated in a Selas type furnace at temperatures ranging from 680 to 860°C. The sheet was then cooled in a controlled atmosphere to about 430°C and then introduced into a seven-ton zinc bath. The sheet was then nitrogen-gas wiped at the exit, jet cooled and finally coiled. Depending on test conditions the speed of the sheet varied in the range 10 to 30 m/min.
[0023] Several coils were galvanized with a bath containing Zn-5% by weight AI and a cerium mischmetal content from 0.05%-0.001% by weight. The cerium content varied from 0.04% to 0.0008% by weight and the La content was 0.02% to 0.0002% by weight. The resulting coating was bright with a grain size varying from 1 to 5 mm, depending on the cooling conditions, and with thicknesses varying from 5 to 35 mm depending on the gas wiping conditions. The coating was uniform and free of bare spots, uncoated areas or other defects.
[0024] A Zn-5% by weight AI bath containing 0.13% by weight Sn and as above 0.05% of cerium mischmetal was also used in the pilot galvanizing line. The coatings obtained had characteristics similar to those described above with a coating somewhat less bright due to a different spangle behavior. An additional bath containing Zn, 5% by weight Al, 0.13% by weight Sn, 0.05% by weight Pb and about 0.05% by weight Ce + La (added as Ce mischmetal or La mischmetal; or added as a master alloy containing about 20% by weight Zn and 80% by weight La and/or Ce mischmetals; or added as a master alloy containing about 90% by weight AI and 10% by weight La and/or Ce mischmetal) was also used in the pilot galvanizing line. The coatings obtained showed a wide range of thickness, were uniform and again were free of bare spots and uncoated areas.
[0025] It is evident that the pilot plant conditions are mentioned as examples only and that other conditions prevailing in continuous annealing and galvanizing lines as regards furnace type, composition of gas, speeds, wiping methods, etc., can be used with advantage with the zinc bath composition according to the invention. Moreover, bath and coating compositions as described herein may be used in non-continuous (e.g. batch) galvanizing methods.
[0026] 3. Specimens from the above pilot plant trials were subjected to various trials for the evaluation of formability and adherence, the corrosion resistance in various environments, the galvanic protection, and the microstructure.
[0027] The formability and adherence was evaluated by means of bulge tests and Erichsen tests. In both types of tests the coatings obtained with the mischmetal-containing bath exhibited and adherence and formability equivalent to that of standard galvanized coatings. For example a 180° bending gave rise to no cracking and in the Erichsen test a depth of 9 mm was made on 0.25 mm thick sheets without peeling of the coating.
[0028] The corrosion resistance, in a salt spray test, of the Zn-AI coatings containing mischmetal was more than twice that of a standard galvanized coating of the same thickness. For example, with the coatings of the present invention the time to first rusting was about 900 hours instead of 350 hours with a conventional galvanized coating of the same thickness.
[0029] Similarly the corrosion resistance in an environment containing 10 ppm S02 was shown to be at least 50% greater than that of a conventional galvanized coating. The galvanic protection of the Zn-AI mischmetal coating was also determined by examining the progress of corrosion around scratches machined on specimens exposed to a SOz-containing environment. The galvanic protection of the mischmetal-containing Zn-5% AI coating was equal to that of a pure zinc coating and far superior to that of a coating containing Zn-55AI-1.5Si.
1. A protective metal coating adhered to a substrate, said coating comprising at least
about 85% by weight Zn, from about 3% to about 15% by weight AI, and from about 5
ppm to about 1.0% by weight of mischmetal, the percentage of mischmetal being calculated
on the total of Zn and Al.
2. A coating according to claim 1 containing from about 0.01 to about 0.1 % by weight
mischmetal, said percentage being calculated on the total of Zn and Al.
3. A coating according to claim 1, wherein the mischmetal is Ce-mischmetal or La-mischmetal.
4. A coating according to claim 2, wherein the mischmetal is Ce-mischmetal or La-mischmetal.
5. A coating according to claim 1, said coating containing additionally at least one
of the elements selected from Fe, Pb, Sb, Mg, Sn, Cu, and Si.
6. A coating according to claim 1, said coating containing additionally antimony.
7. A coating according to claim 6, said coating containing additionally lead.
8. A coating according to claim 7, containing from about 0.03-0.15% by weight Sb and
less than 0.02% by weight Pb.
9. A coating according to claim 1, said coating containing additionally Mg and Pb.
10. A coating according to claim 9, containing from about 0.02-0.15% by weight Mg
and from about 0.02-0.15% by weight Pb.
11. A coating according to claim 10, said coating containing additionally Cu.
12. A coating according to claim 11, containing from about 0.1-0.3% by weight Cu.
13. A coating according to claim 3, wherein said mischmetal is a Ce-mischmetal comprising
from about 45-60% by weight Ce, from about 35 to 50% by weight other rare earths,
and the balance comprising Fe, Mg, Al, Si and impurities.
14. A method of applying a protective metal coating to a substrate comprising the
steps of immersing the substrate in molten alloy comprised of zinc, aluminum and mischmetal,
said bath formulated so as to yield a coating comprising at least about 85% by weight
Zn, from about 3% to about 15% by weight Al, and from about 5 ppm to about 1.0% by
weight of mischmetal, the percentage of mischmetal being calculated on the total of
Zn and Al.
15. A method according to claim 14, wherein said mischmetal is added to the alloy
in the form of a master alloy.
16. A method according to claim 14, wherein said master alloy comprises 20% Zn and
80% by weight mischmetal.
17. A method according to claim 14, wherein said master alloy comprises about 85-90%
by weight AI and about 5-15% by weight mischmetal.
1. Un revêtement métallique protecteur adhérent sur un substrat, ledit revêtement
consistant en au moins environ 85 % en poids de Zn, d'environ 3 à environ 15 % en
poids de AI et d'environ 5 ppm à environ 1,0 % en poids de mischmétal, le pourcentage
de mischmétal étant calculé sur le total de Zn et AI.
2. Un revêtement selon la revendication 1 contenant d'environ 0,01 à environ 0,1 %
en poids de mischmétal, ledit pourcentage étant calculé sur le total de Zn et AI.
3. Un revêtement selon la revendication 1, dans lequel le mischmétal est un mischmétal
au Ce ou un mischmétal au La.
4. Un revêtement selon la revendication 2, dans lequel le mischmétal est un mischmétal
au Ce ou un mischmétal au La.
5. Un revêtement selon la revendication 1, ledit revêtement contenant en outre au
moins un des éléments choisis parmi Fe, Pb, Sb, Mg, Sn, Cu et Si.
6. Un revêtement selon la revendication 1, ledit revêtement contenant en outre de
l'antimoine.
7. Un revêtement selon la revendication 6, ledit revêtement contenant en outre du
plomb.
8. Un revêtement selon la revendication 7, contenant d'environ 0,03 à 0,15 % en poids
de Sb et moins de 0,02 % en poids de Pb.
9. Un revêtement selon la revendication 1, ledit revêtement contenant en outre Mg
et Pb.
10. Un revêtement selon la revendication 9 contenant d'environ 0,02 à 0,15 % en poids
de Mg et d'environ 0,02 à 0,15 % en poids de Pb.
11. Un revêtement selon la revendication 10, ledit revêtement contenant en outre Cu.
12. Un revêtement selon la revendication 11 contenant d'environ 0,1 à 0,3 % en poids
de Cu.
13. Un revêtement selon la revendication 3, dans lequel ledit mischmétal est un mischmétal
au Ce consistant en environ 45-60 % en poids de Ce, d'environ 35 à 50 % en poids d'autres
métaux des terres rares et le reste consistant en Fe, Mg, AI, Si et des impuretés.
14. Un procédé d'application d'un revêtement métallique protecteur sur un substrat
comprenant l'étape d'immersion du substrat dans un alliage fondu consistant en zinc,
aluminium et mischmétal, ledit bain ayant une composition telle qu'il donne un revêtement
consistant en au moins environ 85 % en poids de Zn, d'environ 3 à environ 15 % en
poids de AI et d'environ 5 ppm à environ 1,0 % en poids de mischmetal, le pourcentage
de mischmétal étant calculé sur le total de Zn et AI.
15. Un procédé selon la revendication 14, dans lequel ledit mischmétal est ajouté
à l'alliage sous la forme d'un alliage maître.
16. Un procédé selon la revendication 14, dans lequel ledit alliage maître consiste
en 20 % de Zn et 80 % en poids de mischmétal.
17. Un procédé selon la revendication 14, dans lequel ledit alliage maître consiste
en environ 85-95 % en poids de AI et environ 5-15 % en poids de mischmétal.
1. Auf einem Substrat haftender Schutzüberzug aus Metall, welcher Überzug zumindest
etwa 85 Gew. % Zn, von etwa 3 bis etwa 15 Gew. % AI und von etwa 5 TpM bis et-1,0
Gew. % Mischmetall umfaßt, wobei der Prozentsatz an Mischmetall auf Basis der Summe
von Zn und AI berechnet ist.
2. Überzug nach Anspruch 1, enthaltend etwa 0,01 bis etwa 0,1 Gew. % Mischmetall,
wobei der Prozentsatz an Mischmetall auf Basis der Summe von Zn und AI berechnet ist.
3. Überzug nach Anspruch 1, dadurch gekennzeichnet, daß das Mischmetall Ce-Mischmetall
oder La-Mischmetall ist.
4. Überzug nach Anspruch 2, dadurch gekennzeichnet, daß das Mischmetall Ce-Mischmetall
oder La-Mischmetall ist.
5. Überzug nach Anspruch 1, welcher Überzug zusätzlich zumindest eines der Elemente
ausgewählt aus Fe, Pb, Sb, Mg, Sn, Cu und Si enthält.
6. Überzug nach Anspruch 1, welcher, Überzug zusätzlich Antimon enthält.
7. Überzug nach Anspruch 6, welcher Überzug zusätzlich Blei enthält.
8. Überzug nach Anspruch 7, enthaltend etwa 0,03 bis 0,15 Gew. % Sb und weniger als
0,02 Gew. % Pb.
9. Überzug nach Anspruch 1, welcher Überzug zusätzlich Mg und Pb enthält.
10. Überzug nach Anspruch 9, enthaltend etwa 0,02 bis 0,15 Gew. % Mg und etwa 0,02
bis 0,15 Gew. % Pb.
11. Überzug nach Anspruch 10, welcher Überzug zusätzlich Cu enthält.
12. Überzug nach Anspruch 11, enthaltend etwa 0,1 bis 0,3 Gew. % Cu.
13. Überzug nach Anspruch 3, dadurch gekennzeichnet, daß das Mischmetall Ce-Mischmetall
ist, das etwa 45 bis 60 Gew. % Ce, etwa 35 bis 50 Gew. % andere seltene Erden umfaßt
und wobei der Rest Fe, Mg, Al, Si und Verunreinigungen umfaßt.
14. Verfahren zum Auftragen eines Schutzüberzugs aus Metall auf eine Substrat, dadurch
gekennzeichnet, daß das Substrat in eine flussige Legierung, umfassend Zink, Aluminium
und Mischmetall, getaucht wird, wobei das Bad so formuliert ist, daß es einen Überzug
mit zumindest etwa 85 Gew. % Zn, etwa 3 bis etwa 15 Gew. % AI und etwa 5 TpM bis etwa
1,0 Gew. % Mischmetall ergibt und der Prozentsatz an Mischmetall auf Basis der Summe
von Zn und AI berechnet ist.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß das Mischmetall als Vorlegierung
zur Legierung zugegeben wird.
16. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Vorlegierung 20 Gew.
% Zn und 80 Gew. % Mischmetall umfaßt.
17. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Vorlegierung etwa
85 bis 95 Gew. % AI und etwa 5 bis 15 Gew. % Mischmetall umfaßt.