EP0061407B1 - Verfahren zum Korrigieren der Zusammensetzung eines Zinkbades zum Galvanisieren durch Hinzugabe von zusätzlichen Legierungskonzentraten und Zusammensetzung des Zugabematerials - Google Patents

Verfahren zum Korrigieren der Zusammensetzung eines Zinkbades zum Galvanisieren durch Hinzugabe von zusätzlichen Legierungskonzentraten und Zusammensetzung des Zugabematerials Download PDF

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Publication number
EP0061407B1
EP0061407B1 EP82400522A EP82400522A EP0061407B1 EP 0061407 B1 EP0061407 B1 EP 0061407B1 EP 82400522 A EP82400522 A EP 82400522A EP 82400522 A EP82400522 A EP 82400522A EP 0061407 B1 EP0061407 B1 EP 0061407B1
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EP
European Patent Office
Prior art keywords
alloy
zinc
magnesium
aluminium
beryllium
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.)
Expired
Application number
EP82400522A
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English (en)
French (fr)
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EP0061407A1 (de
Inventor
Noel Dreulle
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.)
AUSTRALIAN MINING AND SMELTING EUROPE Ltd
BILLITON ZINK BV
Metallurgie Hoboken-Overpelt SA
MINARRIA E METALLURGICA DI PERTUSOLA Soc
SAMIM SpA
Asturienne France SA
Societe Miniere et Metallurgique de Penarroya
Norzink AS
Original Assignee
Metallurgie Hoboken-Overpelt SA
Societe des Mines et Fonderies de Zinc de la Vieille Montagne SA
Asturienne France SA
Societe Miniere et Metallurgique de Penarroya
AUSTRALIAN MINING AND SMELTING EUROPE Ltd
MINARRIA E METALLURGICA DI PERTUSOLA Soc
SAMIM SpA
BILLITON ZINK BV
Norzink AS
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Application filed by Metallurgie Hoboken-Overpelt SA, Societe des Mines et Fonderies de Zinc de la Vieille Montagne SA, Asturienne France SA, Societe Miniere et Metallurgique de Penarroya , AUSTRALIAN MINING AND SMELTING EUROPE Ltd, MINARRIA E METALLURGICA DI PERTUSOLA Soc, SAMIM SpA, BILLITON ZINK BV, Norzink AS filed Critical Metallurgie Hoboken-Overpelt SA
Publication of EP0061407A1 publication Critical patent/EP0061407A1/de
Application granted granted Critical
Publication of EP0061407B1 publication Critical patent/EP0061407B1/de
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Classifications

    • 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

  • the invention relates to a process for adjusting the composition of a zinc alloy, intended for the dip galvanizing of steels, including silicon steels, the alloy consisting of zinc of commercial purity with a weighted content. from 1000 to 15000 ppm of lead and as additives of aluminum, tin and magnesium at weight contents selected in the respective ranges (AI) 100 to 5000 ppm, (Sn) 300 to 20 000 ppm, and (Mg) 10 to 1000 ppm, the process consisting in adding, to the molten zinc alloy, deficient in at least one additive, at least one metallic composition, soluble in molten zinc, and comprising with a relatively high content at least one additive in quantity such that the deficit is compensated for.
  • the invention also relates to metallic compositions suitable for implementing the method.
  • Zinc with commercial purity corresponding to AFNOR NFA standards, classes Z6 and Z7 has maximum contents defined in Copper, Cadmium and Iron. In addition, it has maximum lead contents (15,000 p.p.m. for class Z6, 5,000 p.p.m. for class Z7). These lead contents, originally defined by the conditions for the production of zinc, have proved to be favorable for galvanization by lowering the viscosity of the molten zinc, so that they have been maintained while the evolution of the processes metallurgical allows the production of zinc with lead contents lower than 1000 ppm Frequently the categories Z6 and Z7 are currently obtained by adding lead to zinc.
  • the invention therefore proposes a method for adjusting the composition of a zinc alloy, intended for the dip galvanizing of steels, including silicon steels, the alloy consisting of zinc of commercial purity with a weight content of 1 000 to 15000 ppm lead, and as additives, aluminum, tin and magnesium at weight contents selected from the respective ranges (AI) 100 to 5,000 ppm, (Sn) 300 to 20,000 ppm and (Mg) 10 to 1,000 ppm, process according to which we add. to the molten zinc alloy, deficient in at least one additive, at least one metallic composition soluble in the molten zinc and comprising at relatively high content at least one additive, in an amount such that the deficit is compensated for.
  • the magnesium composition is a ternary zinc, magnesium, aluminum alloy with by weight 5000 to 50,000 p: pm of magnesium and 10 to 500 ppm of aluminum
  • the aluminum composition, n added in quantity which takes account of the possible addition of ternary zinc / magnesium / aluminum is a binary zinc / aluminum alloy, with an aluminum content by weight close to 5%.
  • composition chosen from the zinc alloy for galvanization will correspond to the preferred compositions presented by French patent 2,366,376.
  • Nickel and copper are metals to be avoided in the considered galvanizing coatings. Iron could have been tolerated in view of the traces of iron which inevitably dissolve in the alloy during the immersion of steel parts. But beryllium iron alloys hardly dissolve in zinc at 600 ° C.
  • the beryllium supply is obtained using a ternary zinc / aluminum / beryllium alloy, produced by dissolving an aluminum beryllium alloy containing 4-8% beryllium in pure zinc.
  • the weight composition of the ternary alloy is: aluminum 5,000 to 50,000 p.p.m., beryllium aluminum weight ratio 11.5 to 24 and zinc the rest.
  • the term zinc is used here in its usual meaning as a base metal containing common impurities at levels where the properties of the metal, in relation to the intended application, are not appreciably affected.
  • impurities from alloying elements or additives which, at the specified contents, act on the properties of the base metal, in relation to the intended application.
  • the base metal contains, as initial impurity an element which is intended as an additive, at a content significantly higher than that of the initial impurity, the content as an additive is understood to be the sum of the initial content in impurity, and the amount of additive added thereafter.
  • the preferred ternary alloys for supplying magnesium and beryllium respectively have weight compositions of magnesium 30,000 ⁇ 1,500 ppm, aluminum 100 ⁇ 5 ppm, and aluminum 9,000 ⁇ 450 ppm, beryllium 470 ⁇ 50 ppm, in both cases the rest being zinc.
  • zinc which constitutes at least 95% of the alloy by weight, can withstand some losses by oxidation without the composition of the alloy being substantially modified; lead and tin, less oxidizable than zinc, suffer only negligible losses by oxidation.
  • lead and tin less oxidizable than zinc, suffer only negligible losses by oxidation.
  • aluminum and magnesium disappear by oxidation relatively quickly. The readjustment of the composition of the alloy requires preferential additions of aluminum and magnesium.
  • the magnesium oxidizes in depth, and is close to its spontaneous ignition temperature in the air. Moreover, for the normal development of the galvanizing alloy, one operates so as to minimize the oxidation of aluminum and magnesium by preventing them from being in contact with air.
  • each of the metal compositions used be assigned to a particular additive metal, in the sense that the concentration of the additive targeted in the composition must be much higher than the concentration in the alloy, while the concentration ratios of the other metals in the composition are not too far from what they are in the alloy or at least that the concentration ratios of the constituents of the composition compared to that of the targeted additive are significantly lower than the ratios in the alloy.
  • aluminum there is a zinc aluminum alloy 5% by weight of aluminum, its composition corresponding to the eutectic at melting point 385 ° C., and is therefore suitable as a metallic composition assigned to aluminum. .
  • magnesium there is a zinc / magnesium eutectic at 3% by weight of magnesium, with a melting point of 367 ° C. , or during transport and essential handling.
  • the compositions sufficiently close to the eutectic to have an acceptable melting point (less than about 450 ° C.) are practically also too fragile.
  • the addition of small amounts of aluminum significantly reduced the brittleness of the zinc / magnesium binaries. The effect begins to be felt at 10 p.p.m. (by weight) of aluminum.
  • the presence of aluminum reduces the oxidation of magnesium when the ingot is poured. Around 100 p.p.m.
  • beryllium is felt for very low contents, from 4 p.p.m. (by weight). Beyond 100 p.p.m. it is observed that there occurs, at the usual temperature of the galvanizing baths in operation, a segregation of beryllium which collects on the surface and is evacuated with the dross. It has also been found, from 15 ppm by weight of beryllium, for baths with a relatively high aluminum content, greater than 550 ppm, a synergistic action of aluminum and beryllium on the kinetics of the iron-zinc reaction (formation of intermetallic compounds).
  • This table shows that, even using a binary alloy of composition corresponding to the liquidus at 696 ° C, and cooled sufficiently quickly so that the beryllium remains in supersaturation, the tonnages to be used so that the final alloy is in the range 4- 100 ppm represent from 0.5 to 12.5% of the total mass of the alloy, that is to say for a 150-ton bath, from 0.75 to 18.75 tons. Furthermore, the diffusion of beryllium in molten zinc, at temperatures far from the melting point of beryllium (1 2800C) is slow, and the development of the binary alloy at temperatures above 700 ° C is difficult due in particular to the vapor pressure of zinc (boiling point 910 ° C). The development of such alloys is prohibitive on an industrial scale.
  • Example 2 In the induction furnace used in Example 1, 495 kg of zinc Z9 is melted under a neutral atmosphere. The temperature is raised to around 600 ° C. and 4.75 kg of beryllium aluminum alloy containing 5.25% beryllium are added. The temperature is maintained at 600 ° C. until intimate dispersion of the beryllium aluminum in the zinc, under the action of electromagnetic stirring. Then, as soon as the power is turned off, the alloy is poured into energy-cooled ingot molds.
  • beryllium has also made it possible to somewhat reduce the tin bath contents, since tin is intended in particular to take over from magnesium when the content of the latter metal has lowered in the bath by oxidation, and that beryllium reduces the rate of magnesium oxidation.
  • the consumption of the components of the bath is due, on the one hand, to the sampling of alloy constituting the coverings of part, and on the other hand to the oxidation of some of these components in contact either with the galvanizing flux, or with the air entrained by the parts upon immersion in the molten alloy.
  • alloy compositions may vary within the range of the ranges indicated.
  • numerical value is understood as a central value in a usual range, such as ⁇ 5%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)

Claims (11)

1. Verfahren zum Einstellen der Zusammensetzung einer Zinklegierung, die zum Feuerverzinken von Stählen einschließlich Siliziumstählen, bestimmt ist, wobei die Legierung besteht aus Zink handelsüblicher Reinheit mit einem Gewichtsanteil von 1 000 bis 15 000 ppm Blei und als Additive Aluminium, Zinn und Magnesium mit Gewichtsanteilen, die jeweils gewählt sind in den Bereichen (AI) 100 bis 5 000 ppm, (Sn) 300 bis 20 000 ppm und (Mg) 10 bis 1 000 ppm, wobei man der schmelzflüssigen Zinklegierung, der wenigstens ein Additiv fehlt, wenigstens eine im schmelzflüssigen Zink lösliche metallische Zusammensetzung zugibt, die einen relativ hohen Gehalt an wenigstens einem Additiv in einer Menge derart aufweist, daß das Defizit kompensiert wird, dadurch gekennzeichnet, daß die Zinzusammensetzung aus Metall in praktisch reinem Zustand besteht, die Magnesiumszusammensetzung eine ternäre Legierung aus Zink, Magnesium und Aluminium mit einem Gewichtsverhältnis von 5 000 bis 50 000 ppm Magnesium und 10 bis 500 ppm Aluminium ist und die Aluminium zusammensetzung, die in einer Menge unter Berücksichtigung der evtl. Zugabe des Ternärsystems Zink/Magnesium/Aluminium, eine binäre Zink/Aluminiumlegierung mit einem Gewichtsanteil an Aluminium benachbart 5 % ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Anteilsbereiche der Additive der Zinklegierung sind : (AI) 300 bis 600 ppm, (Sn) 1 000 bis 3 000 ppm, (Mg) 20 bis 200 ppm.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die gewählten Additivanteile im wesentlichen (AI) 370 ppm,'(Sn) 2 500 ppm, (Mg) 100 ppm betragen.
4. Verfahren zum Einstellen der Zusammensetzung einer Zinklegierung, die zum Feuerverzinken von Stählen einschließlich Siliziumstählen bestimmt ist, wobei die Legierung gebildet wird aus Zink handelsüblicher Reinheit mit einem Gewichtsanteil von 1000 bis 15 000 ppm Blei und als Additiv Aluminium, Zinn und Magnesium mit Gewichtsanteilen, die jeweils gewählt sind in den Bereichen : (AI) 100 bis 5 000 ppm, (Sn) 300 bis 20 000 ppm, (Mg) 10 bis 1 000 ppm, wobei man zur schmelzflüssigen Zinklegierung, der wenigstens ein Additiv fehlt. wenigstens eine metallische im schmelzflüssigen Zink lösliche Zusammensetzung zugibt, die einen relativ hohen Gehalt an wenigstens einem Additiv in einer Menge derart enthält, daß das Defizit kompensiert wird, dadurch gekennzeichnet, daß die Zinklegierung als komplementäres Additiv Beryllium mit einem Gewichtsanteil zwischen 7 und 100 ppm enthält, daß die Zinnzusammsetzung das Metall in praktisch reinem Zustand darstellt, die Magnesiumzusammensetzung eine ternäre Zink/Magnesium/Aluminium-Legierung mit einem Gewichtsanteil von 5000 bis 50 000 ppm Magnesium und 10 bis 50 ppm Aluminium ist, daß die Berylliumzusammensetzung eine ternäre Zink/Aluminium/Beryllium-Legierung mit 5 000 bis 50 000 ppm Gewichtsanteil Aluminium ist, wobei das Gewichtsverhältnis Aluminium/Beryllium zwischen 11,5 und 24 liegt und die Aluminiumzusammensetzung, die in einer Menge zugegeben wurde, die den Zusatz an den ternären Legierungen Zink/Magnesium/Aluminium und Zink/Aluminium/Beryllium berücksichtigt eine binäre Zink/Aluminium-Legierung mit einem Gewichtsanteil von Aluminium benachbart 5 % ist.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die gewählten Additvgehalte betragen : Zinn 500 ± 25 ppm, Aluminium 375 ± 25 ppm, Magnesium 60 ± 3 ppm, Beryllium 6,5 ± 0,5 ppm.
6. Ternäre Magnesiumlegierung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 5, gekennzeichnet durch einen Gehalt (Gewicht) von 5 00 bis 50 000 ppm Magnesium und 10 bis 500 ppm Aluminium, wobei der Rest aus Zink besteht.
7. Legierung nach Anspruch 6, dadurch gekennzeichnet, daß sie 30 000 ± 1 500 ppm Magnesium und 100 ± 5 ppm Aluminium enthält.
8. Ternäre Berylliumlegierung zur Durchführung des Verfahrens nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß sie enthält (Gewichtsänteile) 5 000 bis 50 000 ppm Aluminium, Beryllium in einem Gewichtsverhältnis mit dem Aluminium von 1/11,5 bis 1/24, wobei der Rest Zink ist.
9. Legierung nach Anspruch 8, gekennzeichnet durch einen Gehalt (Gewichtsteile) von 9 000 ± 450 ppm Aluminium und 470 ± 50 ppm Beryllium.
10. Verfahren nach Anspruch 5, zur Aufrechterhaltung der Zinkleierung während des Verzinkens der aus Stahl bestehenden Werkstücke, durch Zugabe des Magnesiumlegierungternärsystems nach Anspruch 7 und des Berylliumternärsystems nach Anspruch 9, dadurch gekennzeichnet, daß pro Tonne galvanisierter Werkstücke 2 bis 25 kg des Berylliumternärsystepms und 0,5 bis 5 kg des Magnesiumternärsystems zugesetzt werden.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß pro Tonne galvanisierter Werkstücke 12,5 ± 0,6 kg des Berylliumternärsystems und 1,4 ± 0,07 kg des Magnesiumternärsystems zugesetzt werden.
EP82400522A 1981-03-25 1982-03-23 Verfahren zum Korrigieren der Zusammensetzung eines Zinkbades zum Galvanisieren durch Hinzugabe von zusätzlichen Legierungskonzentraten und Zusammensetzung des Zugabematerials Expired EP0061407B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8105955A FR2502641B1 (fr) 1981-03-25 1981-03-25 Procede pour ajuster la composition d'un alliage de zinc pour galvanisation au trempe, par ajout de compositions metalliques concentrees en additif d'alliage, et compositions d'addition
FR8105955 1981-03-25

Publications (2)

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EP0061407A1 EP0061407A1 (de) 1982-09-29
EP0061407B1 true EP0061407B1 (de) 1985-07-17

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EP82400522A Expired EP0061407B1 (de) 1981-03-25 1982-03-23 Verfahren zum Korrigieren der Zusammensetzung eines Zinkbades zum Galvanisieren durch Hinzugabe von zusätzlichen Legierungskonzentraten und Zusammensetzung des Zugabematerials

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US (1) US4439397A (de)
EP (1) EP0061407B1 (de)
CA (1) CA1177678A (de)
DE (1) DE3264732D1 (de)
FR (1) FR2502641B1 (de)
NO (1) NO820994L (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1335867C (en) * 1988-09-02 1995-06-13 Verdun Hildreth Farnsworth Rare earth and aluminium containing galvanising bath
ZA971076B (en) * 1996-02-23 1997-08-25 Union Miniere Sa Hot-dip galvanizing bath and process.
US6569268B1 (en) 2000-10-16 2003-05-27 Teck Cominco Metals Ltd. Process and alloy for decorative galvanizing of steel
US7182824B2 (en) * 2003-06-17 2007-02-27 Nisshin Steel Co., Ltd. Method of manufacturing zinc alloy ingot

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2195566A (en) * 1938-04-23 1940-04-02 American Zinc Products Company Zinc base alloy
DE810222C (de) * 1950-06-10 1951-08-06 Karl Dipl-Ing Lorenz Verfahren und Einrichtung zum Verzinken von Blechen und Gegenstaenden in aluminiumlegierten Baedern
NL252995A (de) * 1959-08-29
US3164464A (en) * 1961-01-09 1965-01-05 Dow Chemical Co Method of introducing magnesium into galvanizing baths
US3320040A (en) * 1963-08-01 1967-05-16 American Smelting Refining Galvanized ferrous article
FR1396546A (fr) * 1964-03-13 1965-04-23 Vallourec Procédé pour l'alimentation en zinc des cuves de galvanisation et installation pour la mise en oeuvre de ce procédé
US3480465A (en) * 1966-03-30 1969-11-25 Shichiro Ohshima Method of chemically bonding aluminum or aluminum alloys to ferrous alloys
IT1036194B (it) * 1974-06-07 1979-10-30 British Steel Corp Procedimento e dispositivo a lancia di ossigeno per la produzione dell acciaio
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

Also Published As

Publication number Publication date
CA1177678A (fr) 1984-11-13
FR2502641A1 (fr) 1982-10-01
EP0061407A1 (de) 1982-09-29
DE3264732D1 (en) 1985-08-22
FR2502641B1 (fr) 1986-05-23
US4439397A (en) 1984-03-27
NO820994L (no) 1982-09-27

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