EP0996763B1 - Feuerverzinken von reaktionsfähigem stahl - Google Patents

Feuerverzinken von reaktionsfähigem stahl Download PDF

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Publication number
EP0996763B1
EP0996763B1 EP98922555A EP98922555A EP0996763B1 EP 0996763 B1 EP0996763 B1 EP 0996763B1 EP 98922555 A EP98922555 A EP 98922555A EP 98922555 A EP98922555 A EP 98922555A EP 0996763 B1 EP0996763 B1 EP 0996763B1
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EP
European Patent Office
Prior art keywords
vanadium
amount
alloy
titanium
zinc
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Expired - Lifetime
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EP98922555A
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English (en)
French (fr)
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EP0996763A1 (de
Inventor
John Zervoudis
Gary R. Adams
Victor M. Duarte
Michael Gilles
Richard Sokolowski
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Umicore NV SA
Teck Metals Ltd
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Umicore NV SA
Teck Metals Ltd
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Publication of EP0996763A1 publication Critical patent/EP0996763A1/de
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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
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc

Definitions

  • This invention relates to a galvanizing alloy and process and, more particularly, relates to a galvanizing alloy and an immersion galvanization process adapted to control the undesirable effects associated with galvanizing reactive steels.
  • the conventional process for hot dip galvanizing of low carbon steels comprises pretreatment of said steels in a 20% to 30%, by weight, zinc-ammonium-chloride (ZnNH 4 Cl) pre-flux, followed by immersion in molten zinc or zinc allow baths.
  • ZnNH 4 Cl zinc-ammonium-chloride
  • the 'normal' or 'N' coating structure produced on low reactivity steel by conventional hot dip galvanizing processes has well defined, compact alloy (intermetallic) layers.
  • the predominant growth mode in this type of coating is by solid-state diffusion of iron and zinc, and thus well established intermetallic (delta and zeta) layers control the rate of the galvanizing reaction.
  • the diffusion reaction rate decreases as the coating thickness increases, thus permitting predictable, consistent coverage.
  • the normal coating has a bright metallic lustre.
  • Recent developments in the manufacture of low-alloy high-strength steels include continuous casting. In the continuous casting process, it is necessary to add elements that 'kill' or deoxidize the steel i.e. prevent gaseous products which produce porosity. Silicon is commonly employed for this purpose. These steels, as a result, generally contain between 0.01% to 0.3%, by weight, silicon but may include up to or more than about 0.5 wt% silicon and are known as 'reactive steels' or silicon steels.
  • Phosphorus in the steel also affects reactivity having an accepted measure of reactivity that is approximately 2.5 times that of silicon.
  • the silicon content plus 2.5 times the phosphorus content is known as the effective silicon content of the steel.
  • Silicon released from the steel during galvanizing is insoluble in the zeta layer. This creates an instability in the zeta layer and produces thick, porous intermetallic layers.
  • the microstructure is characterized by a very thin and uneven delta layer overlaid by a very thick and porous zeta layer.
  • the porous intermetallic layer allows liquid bath metal to react near the steel interface during the entire immersion period. The result is a linear growth mode with immersion time that allows the formation of excessively thick coatings. These coatings are generally very rough, undesirably thick, brittle and dull in appearance.
  • Steels with silicon levels between 0.05 to 0.15 may also develop a 'mixed' reactivity or 'M' coating.
  • This coating is characterized by a combination of reactive and non-reactive areas on the same steel which is believed to be due to differences in localized silicon levels on the surface of the steel.
  • the galvanizer know the reactivity of the steel beforehand and adjust galvanizing conditions accordingly, both of which are difficult to accomplish in practice. Under some conditions, this process also produces dross that tends to float in the bath and be drawn out on the workpiece, producing unacceptable coatings.
  • the alloy comprises zinc of commercial purity containing by weight 0.1 to 1.5% lead, 0.01 to 0.05% aluminum, 0.03 to 2.0% tin, and 0.001 to 2.0% magnesium.
  • the alloys presented include variations of the PolygalvaTM alloy components of lead, aluminum, magnesium and tin in zinc.
  • a process known as the SupergalvaTM process includes an alloy of zinc containing 5 wt% aluminum. The process requires a special flux and double dipping not generally accepted by commercial galvanizers.
  • Co-Pending US Patent Application No. 08/667,830 filed June 20, 1996 describes a new alloy and process for controlling reactivity in steels with silicon content up to 1 wt%.
  • the alloy comprises zinc of commercial purity containing, by weight, one or both of vanadium in the amounts of at least 0.02% to 0.04% and titanium in the amounts of at least 0.02% to 0.05%.
  • the process should also produce coatings of acceptable and uniform thickness over the full range of steels.
  • Another object of the invention is to provide an alloy and process which uses standard galvanizing equipment operated under normal conditions for galvanizing steels of mixed reactivity without the need to adjust for variations in steel chemistry.
  • the process of the invention for galvanizing steel, including reactive steels, by immersion comprises immersing said steel in a molten bath of a zinc alloy comprising, by weight, aluminum in the amount of at least 0.001% to 0.007%, preferably 0.002% to 0.004%, tin in the amount of at least 0.5% to a maximum of 2%, preferably at least 0.8%, and one of an element selected from the group consisting of vanadium in the amount of at least 0.02%, preferably 0.05% to 0.12%, titanium in the amount of at least 0.03%, preferably 0.06% to 0.10%, and both vanadium and titanium together in the amount of at least 0.02% vanadium and at least 0.01% titanium for a total of at least 0.03%, preferably 0.05 wt% to 0.15%, of vanadium and titanium, the balance zinc containing up to 1.3 wt% lead.
  • a zinc alloy comprising, by weight, aluminum in the amount of at least 0.001% to 0.007%, preferably 0.002% to
  • the alloy of the invention for galvanizing steel comprises, by weight, aluminum in the amount of at least 0.001% to 0.007%, preferably 0.002 to 0.004%, tin in the amount of at least 0.5% to a maximum of 2%, preferably at least 0.8%, and one of an element selected from the group consisting of vanadium in the amount of at least 0.02%, preferably 0.05% to 0.12%, titanium in the amount of at least 0.03%, preferably 0.06% to 0.10%, and both vanadium and titanium together in the amount of at least 0.02% vanadium and at least 0.01% titanium for a total of at least 0.03%, preferably 0.05% to 0.15%, of vanadium and titanium, the balance zinc containing up to 1.3 wt% lead.
  • the alloy may comprise, by weight, aluminum in the amount of at least 0.001%, tin in the amount of 0.5% to 2%, and vanadium with nickel in the amount of at least 0.02% vanadium and at least 0.02% nickel to a maximum of 0.15% vanadium and nickel collectively.
  • Titanium may be added in an amount of at least 0.01 % titanium to a maximum of 0.2% vanadium, nickel and titanium.
  • the alloy for use in a zinc alloy bath, is comprised of aluminum in the amount of at least 0.001%, tin in the amount of about 0.5% to about 2%, vanadium in the amount of 0.02 to 0.12%, bismuth in the amount of 0.05% to 0.1%, and the balance zinc.
  • curve 10 typifies the variation of thickness in microns of a coating of zinc of commercial purity, such as conventional Prime Western (PW), on a steel surface as a function of the silicon content of the steel.
  • commercial purity used herein will be understood to include Prime Western, High Grade and Special High Grade zinc.
  • the thickness of zinc coating peaks at a thickness of about 260 microns at a silicon content of about 0.15 wt%, decreases to a thickness of about 175 microns at a silicon content of about 0.2 wt%, and then increases to a maximum thickness of about 375 microns at a silicon content of about 0.5 wt%, decreasing in thickness slightly to a silicon content of 1.0 wt%.
  • This curve 10 will be recognized as being very similar to the well-known Sandelin Curve.
  • the composition of the steels used is listed in Table 1 below.
  • vanadium alone is an effective alloying element for reducing the reactivity of silicon steels with up to 0.25 wt% Si. Vanadium in the bath is believed to combine with the silicon to form vanadium silicides as inert particles that become dispersed in the zeta layer. The silicon-free iron can then react with zinc to form a very compact and smooth layer that prevents liquid bath metal from reaching the delta layer. In essence, the vanadium effectively suppresses reactivity by stabilizing the growth of the zeta layer in the coating, which controls the growth rate by a diffusion process.
  • tin is also an effective element for reducing the reactivity of steels.
  • Tests have shown that a galvanizing bath containing 2.5 wt% to 5 wt% tin can control reactivity in steels with up to 1% silicon content.
  • tests have also shown that tin in amounts greater than 2 wt% react rapidly with the galvanizing kettle wall steel at galvanizing temperatures. When the tin level in the galvanizing bath is below 2%, the reaction with the kettle steel proceeds at a slow rate, which is comparable to that of the commercial grade zinc.
  • the level of tin in a galvanizing bath is 2%, the presences of tin controls reactivity in steels with only up to 0.3% silicon.
  • Zinc of commercial purity such as conventional Prime Western, contains up to 1.3 wt% lead, typically about 0.8% lead.
  • other grades of zinc available such as High Grade and Special High Grade have lower contents of lead.
  • There is a growing tendency to reduce and eliminate the presence of lead in galvanizing because of environmental, health and safety concerns. It has been observed that bare spots in galvanized coatings could be produced from galvanizing baths without lead or with reduced lead contents at lower levels of tin at about 1 wt% tin with 0.05 wt% vanadium and 0.002 wt% aluminium on steels having lower silicon contents.
  • titanium is used in place of vanadium.
  • Tests have shown in a galvanizing bath containing 1.8 wt% tin, 0.002 wt% aluminum and the balance zinc of commercial purity, the presence of 0.06 wt% and 0.10 wt% titanium effectively controls reactivity to varying degrees in steels having silicon contents up to about 0.5 wt %, as shown by Sn-Ti curve 13 in Figure 2.
  • Increasing the titanium content in the galvanizing bath to 0.1 wt% did not increase the maximum silicon level controlled as seen by Sn-Ti curve 14 in Figure 2.
  • the titanium addition to the bath forms a ternary Zn-Fe-Ti intermetallic which increases the amount of dross and ash during galvanizing and contributes to high rates of titanium consumption or depletion in the bath. It also adversely affects the appearance of the galvanized coating by eliminating the distinctive large spangle formed with the tin-vanadium alloy which most galvanizing customers favour.
  • Small amounts of titanium added to the tin-vanadium alloy as a substitute for a portion of the vanadium can be used to lower the level of vanadium in the alloy, without the adverse effects of the high titanium-tin alloy.
  • An other embodiment of the alloy composition of the invention has utility in zinc-nickel alloy baths containing a typical nickel content of 0.05 wt% to 0.08 wt% nickel, and up to 0.1 wt% nickel, and comprises aluminum in the amount of at least 0.001 wt%, tin in the amount of about 0.5 wt% to about 2 wt%, and vanadium with nickel in the amount of at least 0.02 wt% vanadium and at least 0.02 wt% nickel to a maximum of 0.15 wt% vanadium and nickel collectively.
  • the alloy compositions and the process of the invention will now be described with reference to the following non-limitative examples.
  • composition of alloy No. 2 (Sn-Ni) is a high tin alloy.
  • composition of alloy No. 3 (V-Ti) is included in US Patent Application No. 08/667,830.
  • composition of alloy No. 4 (Sn-V) is an embodiment of alloy of the subject Patent Application.
  • the samples were removed after approximately 2, 4, 7 and 11 days immersion.
  • the coatings on the samples were removed by immersion in hot sodium hydroxide solution, followed by cold hydrochloric solution, and re-weighed.
  • a bench scale line was set up to process the test samples consistently. The following steps were taken: 1. Degreasing 0.25 g/cc NaOH solution at 70°C with agitation for ten minutes 2. Rinse Tepid flowing water 3. Pickling 15 wt% Hcl at room temperature, inhibited with RodineTM 85 (1:4000), for 20 minutes 4. Pre-flux 20 wt% ZaclonTM K (ZnNH 4 Cl) at 60°C, for two minute immersion. 5. Drying Oven-dried for five minutes at 110°C.
  • melts were prepared in a SiC crucible that provided a galvanizing surface of 150 mm in diameter.
  • the crucible was heated in a radiant tube furnace.
  • the galvanizing temperature was 450 ⁇ 2°C.
  • the melt surface was skimmed prior to immersion and just before the test coupons were withdrawn.
  • the test coupons were dipped for eight-minute immersions.
  • the immersion rate was 40 mm/sec while the withdrawal rate was 60 mm/sec.
  • the samples were air-cooled at room temperature (no quenching).
  • Hot-rolled low-carbon silicon-killed steel coupons measuring 77 mm x 39 mm x 3 mm, were used.
  • This table includes the respective Si-equivalent or Si + 2.5P level for the steels, which takes into account the weighted effect of phosphorus as it relates to the reactivity behaviour of the steel.
  • the test coupons were photographed and classified under one of the three following categories: Normal, Reactive or Mixed.
  • a description for each category of coating appearance is as follows: Normal The typical coating of a low-reactivity steel, usually bright and relatively smooth with visible spangle.
  • Reactive The typical coating of a reactive steel, usually matte-grey with no visible spangle.
  • Mixed The typical coating of a steel that has both reactive and non-reactive areas. The coating is usually very rough and varies from thin in low-reactivity areas to thick in the reactive areas.
  • Coating thickness measurements were made using an electromagnetic thickness gauge. The coating thickness results are presented in graph form in Figures 1 to 3 and constitute the steel reactivity curves.
  • test samples Twenty-five mm long pieces were cut from representative areas of the test coupons and prepared by conventional metallographic techniques for microscopic examination. All test samples were examined by optical microscopy. Selected samples were examined with a scanning electron microscope (SEM) and energy dispersive x-ray micro-analysis (EDS) was performed on selected samples as required.
  • SEM scanning electron microscope
  • EDS energy dispersive x-ray micro-analysis
  • the maximum effective silicon level controlled is about 0.3 wt%.
  • 0.5 wt% effective silicon can be controlled with a minimum level of 0.04 wt% vanadium and a tin level of 1.8 wt% (which is near the maximum allowable level), and with a minimum level of 0.4 wt% tin and a 0.12 wt% vanadium level.
  • a preferred composition for controlling the 0.5 wt% Si level is 1.0 wt% tin with 0.05 wt% vanadium.
  • the 1.0 wt% effective silicon can be controlled with a preferred composition of 1.2 wt% tin and 0.08 wt% vanadium.
  • the maximum effective silicon level that was controlled was 0.5 wt%, even when the maximum allowable amount of 1.8 wt% tin and an amount of 0.1 wt% titanium were added to the galvanizing bath.
  • Trials were conducted on 77 mm x 39 mm x 3 mm low silicon steel coupons which were pretreated by an acetone rinse and scrubbing, pickling in 15% HCL solution for 10 - 15 minutes, preflux of ZACLON KTM (20° Be) for 2 minutes at 70°C and oven-dried at 100 °C for 5 minutes.
  • the coupons were galvanized by immersion for 4 minutes in zinc alloy baths of Special High Grade 25 kg melt saturated with iron and containing 0.004 wt% aluminum, 1 wt% tin, 0.05 wt% vanadium and varying amounts of bismuth at a temperature of 450° C.
  • the presence at least 0.05 wt% bismuth was found to be effective in obviating bare spots and in enhancing spangling of the galvanized coating.
  • An upper limit of bismuth of 0.1 wt% bismuth was found economically viable, amounts in excess of 0.1% up to 0.5% did not improve the quality of coating.
  • Galvanized coatings produced in accordance with the invention are complete and uniform and of desired thickness on low and high silicon steels including steel having silicon content from 0.01 wt% to at least 0.5 wt%.
  • the coatings produced also have a bright metallic lustre.
  • the process can be easily adapted to conventional galvanizing production equipment using normal galvanizing temperatures and immersion times.

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Claims (18)

  1. Legierung zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Aluminium in einer Menge von 0,001 bis 0,007 %, Zinn in einer Menge von 0,5 bis 2 % und ein Element aus der Gruppe Vanadium in einer Menge von 0,02 bis 0,12 %, Titan in einer Menge von 0,03 bis 0,10 % und Vanadium und Titan zusammen in einer Menge von mindestens 0,02 % Vanadium und mindestens 0,01 % Titan bei einem Gesamtgehalt an Vanadium und Titan von 0,03 bis 0,15 %, sowie gegebenenfalls Wismut in einer Menge von 0,05 bis 0,5 %, wobei der Rest aus Zink mit einem Gehalt an bis zu 1,3 % Blei besteht.
  2. Legierung nach Anspruch 1 zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Vanadium in einer Menge von 0,05 bis 0,12 %.
  3. Legierung zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Aluminium in einer Menge von 0,001 bis 0,007 %, Zinn in einer Menge von 0,5 bis 2 %, Vanadium in einer Menge von 0,02 bis 0,12 % und gegebenenfalls Wismut in einer Menge von 0,05 bis 0,5 %, wobei der Rest aus Zink mit einem Gehalt an bis zu 1,3 Gew.-% Blei besteht.
  4. Legierung nach Anspruch 3 zum Verzinken von Stahl, zusätzlich enthaltend, bezogen auf das Gewicht, Wismut in einer Menge von 0,05 bis 0,1 %.
  5. Legierung nach Anspruch 1 zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Titan in einer Menge von 0,06 bis 0,10 %.
  6. Legierung nach Anspruch 1, wobei die Zinklegierung, bezogen auf das Gewicht, mindestens 0,03 % Vanadium und Titan enthält, wenn Vanadium und Titan zusammen vorliegen, wobei das Vanadium in einer Menge von mindestens 0,02 % und das Titan in einer Menge von mindestens 0,01 % vorliegen und wobei Vanadium und Titan zusammen maximal 0,15 % ausmachen.
  7. Legierung nach Anspruch 6, wobei Vanadium und Titan gemeinsam in einer Menge von mindestens 0,05 Gew.-% vorliegen.
  8. Legierung zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Aluminium in einer Menge von 0,001 bis 0,007 %, Zinn in einer Menge von 0,5 bis 2,0 % und Vanadium und Nickel in einer Menge von mindestens 0,02 % Vanadium und mindestens 0,02 % Nickel bis maximal 0,15 % Vanadium und Nickel zusammen, wobei der Rest aus Zink mit einem Gehalt an bis zu 1,3 Gew.-% Blei besteht.
  9. Legierung zum Verzinken von Stahl, enthaltend, bezogen auf das Gewicht, Aluminium in einer Menge von 0,001 bis 0,007 %, Zinn in einer Menge von 0,5 bis 2,0 %, Vanadium in einer Menge von 0,02 bis 0,12 % und Wismut in einer Menge von 0,05 bis 0,5 %, wobei der Rest aus Zink besteht.
  10. Verfahren zum Verzinken von Stahl durch Eintauchen in ein Zinklegierungs-Verzinkungsbad, umfassend die folgende Stufe:
    Eintauchen des Stahls in ein geschmolzenes Bad einer Zinklegierung, die, bezogen auf das Gewicht, 0,001 bis 0,007 % Aluminium, 0,5 bis 2 % Zinn und eine zur Verringerung der Reaktivität des Stahls wirksame Menge mindestens eines Elements aus der Gruppe 0,02 bis 0,12 % Vanadium, 0,03 bis 0,10 % Titan und mindestens 0,02 % Vanadium und mindestens 0,01 % Titan, bei einem Gesamtgehalt an Vanadium und Titan von 0,03 bis 0,15 %, und gegebenenfalls 0,05 bis 0,5 Gew.-% Wismut, wobei der Rest aus Zink mit einem Gehalt an bis zu 1,3 Gew.-% Blei besteht.
  11. Verfahren nach Anspruch 10, wobei die Zinklegierung mindestens 0,05 Gew.-% Vanadium enthält.
  12. Verfahren nach Anspruch 10, wobei die Zinklegierung 0,05 bis 0,12 Gew.-% Vanadium enthält.
  13. Verfahren nach Anspruch 10, wobei die Zinklegierung mindestens 0,06 Gew.-% Titan enthält.
  14. Verfahren nach Anspruch 10, wobei die Zinklegierung 0,06 bis 0,10 Gew.-% Titan enthält.
  15. Verfahren zum Verzinken von Stahl durch Eintauchen in ein Bad aus einer Zink-Nickel-Legierung, umfassend die folgende Stufe:
    Eintauchen des Stahls in ein geschmolzenes Bad aus einer Zink-Nickel-Legierung, die, bezogen auf das Gewicht, 0,001 bis 0,007 % Aluminium, 0,5 bis 2 % Zinn und Vanadium und Nickel in einer Menge von mindestens 0,02 % Vanadium und mindestens 0,02 % Nickel bis zu einem maximalen Gesamtgehalt an Vanadium und Nickel von 0,15 % und gegebenenfalls 0,05 bis 0,5 % Wismut enthält, wobei der Rest aus Zink mit einem Gehalt an bis zu 1,3 Gew.-% Blei besteht.
  16. Verfahren nach Anspruch 15, wobei die Legierung zusätzlich mindestens 0,01 % Titan enthält, wobei der maximale Gesamtgehalt an Vanadium, Nickel und Titan 0,2 % beträgt.
  17. Verfahren zum Verzinken von Stahl durch Eintauchen in ein Zinklegierungs-Verzinkungsbad, umfassend die folgende Stufe:
    Eintauchen des Stahls in ein geschmolzenes Bad einer Zinklegierung, die, bezogen auf das Gewicht, 0,001 bis 0,007 % Aluminium, 0,5 bis 2,0 % Zinn, 0,02 bis 0,12 % Vanadium und 0,05 bis 0,5 % Wismut enthält, wobei der Rest aus Zink besteht.
  18. Verfahren nach Anspruch 17, wobei das geschmolzene Zinkbad 0,05 bis 0,1 % Wismut enthält.
EP98922555A 1997-06-06 1998-05-22 Feuerverzinken von reaktionsfähigem stahl Expired - Lifetime EP0996763B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US87016497A 1997-06-06 1997-06-06
US870164 1997-06-06
PCT/CA1998/000506 WO1998055664A1 (en) 1997-06-06 1998-05-22 Galvanizing of reactive steels

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EP0996763A1 EP0996763A1 (de) 2000-05-03
EP0996763B1 true EP0996763B1 (de) 2004-04-07

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EP98922555A Expired - Lifetime EP0996763B1 (de) 1997-06-06 1998-05-22 Feuerverzinken von reaktionsfähigem stahl

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EP (1) EP0996763B1 (de)
AT (1) ATE263850T1 (de)
AU (1) AU730209B2 (de)
CA (1) CA2293495C (de)
DE (1) DE69823032T2 (de)
ES (1) ES2217555T3 (de)
WO (1) WO1998055664A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0852264A1 (de) * 1997-01-02 1998-07-08 Industrial Galvanizadora S.A. Zinklegierungen, die antikorrosive Beschichtungen auf eisenhaltigen Werkstoffen liefern
CZ297569B6 (cs) * 1997-05-23 2007-02-07 Umicore Slitina a zpusob zinkování oceli ponorem
US6569268B1 (en) * 2000-10-16 2003-05-27 Teck Cominco Metals Ltd. Process and alloy for decorative galvanizing of steel
FR2894255B1 (fr) * 2005-12-01 2008-04-04 Electro Rech Sarl Bain de galvanisation a chaud de pieces en une nuance d'acier quelconque
DE102010031439A1 (de) * 2010-07-16 2012-01-19 Aktiebolaget Skf Wälzlager und Verfahren zur Beschichtung eines Bauteils eines Wälzlagers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2366376A1 (fr) * 1976-10-01 1978-04-28 Dreulle Noel Alliage destine a la galvanisation au trempe d'aciers, y compris aciers contenant du silicium, et procede de galvanisation adapte a cet alliage
JP2918434B2 (ja) * 1993-11-30 1999-07-12 富士電気化学株式会社 電池の負極亜鉛缶

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ES2217555T3 (es) 2004-11-01
DE69823032D1 (de) 2004-05-13
EP0996763A1 (de) 2000-05-03
CA2293495A1 (en) 1998-12-10
AU7517198A (en) 1998-12-21
DE69823032T2 (de) 2005-04-28
WO1998055664A1 (en) 1998-12-10
ATE263850T1 (de) 2004-04-15
CA2293495C (en) 2006-01-03
AU730209B2 (en) 2001-03-01

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