EP0095402A1 - Verfahren und Legierung zur Feuerverzinkung von Silicium enthaltenden Stählen und verzinkte Gegenstände - Google Patents

Verfahren und Legierung zur Feuerverzinkung von Silicium enthaltenden Stählen und verzinkte Gegenstände Download PDF

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Publication number
EP0095402A1
EP0095402A1 EP83400916A EP83400916A EP0095402A1 EP 0095402 A1 EP0095402 A1 EP 0095402A1 EP 83400916 A EP83400916 A EP 83400916A EP 83400916 A EP83400916 A EP 83400916A EP 0095402 A1 EP0095402 A1 EP 0095402A1
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EP
European Patent Office
Prior art keywords
bath
weight
germanium
steel
layer
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.)
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Application number
EP83400916A
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English (en)
French (fr)
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EP0095402B1 (de
Inventor
Jean-Louis Caillerie
Rémy Decaens
Armand Limare
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.)
Societe Miniere et Metallurgique de Penarroya
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Societe Miniere et Metallurgique de Penarroya
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Priority to AT83400916T priority Critical patent/ATE26308T1/de
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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to the galvanization of objects formed from steel, in particular of a type containing silicon at a concentration of up to 0.45% by weight. More specifically, the invention relates to a galvanizing process, galvanized objects formed by its implementation, as well as an alloy used for the implementation of this process.
  • Hot dip galvanizing of steels containing less than 0.04% by weight of silicon does not pose significant problems concerning the quality of the coating formed.
  • the main properties of the coatings formed are a shiny appearance, good corrosion resistance, good adhesion to the substrate and a thickness of the order of 70 to 90 and up to 120 micrometers.
  • French Patent No. 8 76-29.545 describes a galvanizing process suitable for treating steel having a low to medium silicon content, which can reach 0.2% by weight at most. This process requires, before the actual galvanization, a very careful treatment of the surfaces, including in particular an additional pickling operation with concentrated hydrochloric acid, in addition to the conventional processes.
  • the alloy bath used for this galvanizing contains aluminum, in an amount up to 0.5% by weight, magnesium in an amount up to 0.1% by weight and tin in an amount up to 2% by weight. weight.
  • This process although it constitutes an important advance and that it is used on an industrial scale for the galvanization of semi-quenched and quenched silicon steels, however has certain drawbacks, in particular those related to the low fluidity of the bath. In particular, it often causes significant flow restraint and the filling of small holes formed in the parts. In addition, the flags and drops that often form at the edge of the pieces mean that they must be taken up before marketing. Finally, this process requires the temperature to be fixed at a value at least equal to 450 ° C., which causes the formation of a large quantity of ash.
  • This process certainly allows the galvanization of steels containing up to 0.2% silicon with thicknesses greater than or equal to the standards in force, without having to maintain a narrow range of aluminum in the molten bath. It is not the same when we want to galvanize steels containing more than 0.2% silicon.
  • the invention relates to a galvanizing process which, unlike the aforementioned process, is suitable even for parts with a high silicon content of up to 0.45% by weight of silicon, in the presence of a small amount of germanium incorporated in the bath.
  • the bath also advantageously comprises lead and possibly aluminum. It is found in fact that germanium has a significant influence on the reactions of the iron-zinc couple, in the presence or absence of aluminum. It is further noted that the combination of lead and germanium gives the galvanizing bath a very high fluidity and surface tension which allow the implementation of the galvanization at a lower temperature than that which is commonly used, in particular close to 440 *VS.
  • the invention relates to a method of galvanizing steel objects, of the type which comprises treating the surface of the objects to be galvanized, then immersing them in a galvanizing bath; this process includes adjusting the composition of the bath so that it contains 0.005 to 0.2% by weight of germanium, and adjusting the temperature of the bath to a value between about 440 and 460 . C, preferably between 440 and 450 . vs.
  • composition of the bath is advantageously adjusted so that the bath contains 0.5 to 1.5% by weight of lead, and preferably also 0.001 to 0.05% by weight of aluminum.
  • the composition of the galvanizing bath is adjusted so that this bath contains, in weight percentages, 0.03 to 0.15% germanium and 0.8 to 1.2% lead, advantageously in the presence from 0.001 to 0.01% aluminum.
  • This adjustment of the composition of the bath is preferably carried out by adding suitable quantities of at least one master alloy.
  • the surface treatment prior to immersion in the galvanizing bath, advantageously only comprises the normal operations of surface treatment before galvanization, in particular degreasing, pickling, rinsing and fluxing.
  • the invention also relates to articles of galvanized steel, of the type which comprises a body of effervescent steel, semi-calmed or calmed with silicon, forming a substrate, and a galvanized coating with a laminated structure comprising, from of the substrate, a layer of intermetallic iron and zinc compounds, and a layer having substantially a constant composition; the layer of intermetallic compounds contains germanium whose concentration varies in the thickness of this layer, this concentration being maximum on the one hand at a distance from the interface of the substrate and the layer of intermetallic compounds and on the other hand at a distance of the interface of this layer of intermetallic compounds and of the layer of substantially uniform composition.
  • the invention also relates to an object of galvanized steel, comprising a body of steel quenched with silicon or with a high silicon content, up to 0.45% by weight, this body forming a substrate, and a galvanizing coating with structure.
  • polyphase in which 0.005 to 0.2% germanium is dispersed practically throughout its thickness.
  • the thickness of the coating formed on these galvanized steel objects is advantageously between 60 and 120 micrometers.
  • the invention also relates to an alloy intended for the implementation of the abovementioned method, that is to say for the dip galvanization of steel objects whose silicon content is less than 0.45%, this alloy containing, in addition to zinc and in weight percentages, 0.5 to 1.5% lead, 0.005 to 0.2% germanium and 0.001 to 0.05% aluminum.
  • this alloy contains, in weight percentages, 0.9 to 1.2% of lead, 0.03 to 0.15% of germanium and 0.001 to 0.01% aluminum.
  • Figure 1 is a schematic section, at a magnification of about 1000, of a part of a galvanized object according to the invention.
  • This object comprises a substrate 1 of steel, for example of a semi-calm or calm steel.
  • This substrate carries a coating which comprises a layer 2 of intermetallic compounds and an outer layer 3 whose surface has not been shown and which has a substantially uniform composition.
  • Layer 2 is represented with two sublayers 4 and 5 with different crystallographic characteristics.
  • FIG. 2 represents the variation of the concentration of germanium in the layer of intermetallic compounds represented in FIG. 1.
  • the abscissae correspond to the distances measured from the sublayer 6.
  • Curve 7 represents the variation of the concentration of germanium in the case of an object galvanized for a short immersion time, for example of the order of one minute at 440 "C. In this case, the maximum of the concentration is found in the under-layer 4.
  • the germanium distribution curve, identified by the reference 8 in FIG. 2 indicates a maximum concentration in the sublayer 5.
  • this maximum is found in one of the sublayers 4 and 5, in general close to their interface, but always in the layer of intermetallic compounds 2 and at a distance from the interfaces. on the one hand with the body 1 of steel and on the other hand with the outer layer 3 of substantially uniform composition.
  • germanium This behavior of germanium is original insofar as on the one hand the technical literature does not refer to it and on the other hand this behavior is distinguished from that of other elements of addition of zinc baths, and in particular of that of aluminum. It is known that this reduces the reactivity of zinc vis-à-vis silicon steels. In particular, it has been found that the aluminum additions modify the reaction kinetics, and in particular its order. On the contrary, germanium appears to have only a very limited effect on the order of the reaction kinetics.
  • Germanium diffuses in following on either side of this interface, as the layer 2 of intermetallic compounds is formed on either side; diffusion can ultimately cause a nearly uniform distribution of germanium when the immersion time is long enough, especially in the presence of a large amount of silicon which accelerates the reactions.
  • the scope of the invention is in no way limited by this interpretation.
  • the alloy has a fluidity and a surface tension which are excellent so that the temperature of the bath can be maintained at 440 ° C only, then that the temperature usually required is 450 to 470 ° C.
  • the dripping of the rooms poses hardly any problems thanks to the fluidity of the bath.
  • the coatings have exceptional shine and have excellent adhesion to the substrate.
  • the thickness of zinc coatings on steels containing more than 0.2% is generally less than 70 micrometers and almost independent of the residence time in the zinc bath and commonly used galvanizing temperatures.
  • germanium in increasing quantity in the zinc bath containing 400 to 500 grams per ton of aluminum increases the thickness of the zinc coatings obtained on steels to more than 0.2% of silicon.
  • germanium therefore has an effect beneficial on galvanizing steels with more than 0.2% silicon in a zinc or alloy bath containing aluminum.
  • This zinc containing lead and germanium allows a reduction in the galvanizing temperature of the order of ten degrees without altering the productivity of the galvanizer which, in the case of a conventional zinc without germanium is in generally limited to a temperature of 450 ° C when it galvanizes loads of significant weight compared to the volume of zinc contained in the tank.
  • the combination of elements Pb, Ge, A1 in the alloy makes it possible to galvanize practically any type of steel at temperatures of 440 to 450 ° C approximately with thicknesses ranging between 70 and 200 micrometers.
  • the aluminum content should be between 250 and 350 grams per tonne while at 450 ° C, aluminum should be between 400 and 500 grams per tonne.
  • 100 ⁇ 100 millimeter test pieces having a thickness of 3 to 5 millimeters are used, formed from three different grades of steel, steel A being of effervescent type, steel B being a steel quenched with silicon. , and steel C being a steel with a high silicon content. More specifically, the designation of these steels is as follows:
  • test pieces undergo, before the actual galvanization, that is to say the immersion in the bath of molten zinc, a conventional surface treatment.
  • This treatment first comprises a degreasing at 70 ° C in an aqueous solution at 50 grams per liter of NaOH and 50 grams per liter of Na 2 C0 3 .
  • the test pieces are then rinsed with running water at room temperature.
  • test pieces are then undergo pickling in commercial hydrochloric acid at 50%, in the presence of a well known inhibitor "Socospar” C 51, for 30 to 45 minutes. Then, the test pieces are rinsed with running water at room temperature.
  • the following treatment operation is a fluxing at 80 ° C, in a solution of 200 grams per liter of zinc chloride and 200 grams per liter of NH 4 Cl.
  • the test pieces are then dried in an oven at 100 ° C and are ready to be used for galvanizing
  • the galvanization is carried out by immersing the test pieces, for the times indicated, in a bath contained in a 50 kg crucible, having a capacity of one ton.
  • the temperature of the galvanizing bath is indicated for each example and it is adjusted to plus or minus 2 ° C.
  • composition of the galvanizing baths is indicated in the table below.
  • the coating has a suitable thickness and appearance only in the case of effervescent steels.
  • the coating has a large thickness which continues to grow even after long periods of immersion, and it has a gray or mottled appearance. These coatings are much too thick when the immersion time is long.
  • Example 3 all the coatings obtained in Examples 3, 4 and 5, that is to say made according to the invention, have a shiny appearance. Their thicknesses are suitable for conventional galvanizing coatings. However, in Example 4, the thicknesses obtained with steels B and C are excessive for the only immersion time tested. This too great thickness is attributed to a too high reactivity, due to the temperature of 450 ° C. which proves to be too high in the case of these test conditions. Consequently, it is preferable that the temperature of the bath be reduced to 440 ° C. Example 5 differs from Example 4 only in this reduction in temperature. It is then noted that, even in the case of calm steels and with a high silicon content, the coatings obtained have a thickness which is perfectly suitable under industrial operating conditions.
  • galvanized objects is excellent because not only is the coating shiny, but the latter also does not form drops or flags along the edges of the objects.

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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)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
EP83400916A 1982-05-05 1983-05-05 Verfahren und Legierung zur Feuerverzinkung von Silicium enthaltenden Stählen und verzinkte Gegenstände Expired EP0095402B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83400916T ATE26308T1 (de) 1982-05-05 1983-05-05 Verfahren und legierung zur feuerverzinkung von silicium enthaltenden staehlen und verzinkte gegenstaende.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8207772 1982-05-05
FR8207772A FR2526445A1 (fr) 1982-05-05 1982-05-05 Procede et alliage de galvanisation au trempe d'acier et objet galvanise

Publications (2)

Publication Number Publication Date
EP0095402A1 true EP0095402A1 (de) 1983-11-30
EP0095402B1 EP0095402B1 (de) 1987-04-01

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EP83400916A Expired EP0095402B1 (de) 1982-05-05 1983-05-05 Verfahren und Legierung zur Feuerverzinkung von Silicium enthaltenden Stählen und verzinkte Gegenstände

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US (2) US4636354A (de)
EP (1) EP0095402B1 (de)
JP (1) JPS58207363A (de)
AT (1) ATE26308T1 (de)
CA (1) CA1193154A (de)
DE (1) DE3370654D1 (de)
ES (1) ES522090A0 (de)
FR (1) FR2526445A1 (de)
GR (1) GR79280B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2097784C (en) * 1993-06-04 1997-03-04 Martin Gagne Alloy for after-fabrication hot-dip galvanizing
US5849408A (en) * 1993-12-27 1998-12-15 Nippon Mining & Metals Co., Ltd. Hot-dip zinc plating product
CN100362123C (zh) * 2006-02-16 2008-01-16 无锡麟龙铝业有限公司 一种镀锌钢板的镀覆材料及其生产方法
US20100304184A1 (en) * 2009-06-01 2010-12-02 Thomas & Betts International, Inc. Galvanized weathering steel

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3245765A (en) * 1962-03-08 1966-04-12 Armco Steel Corp Process of improving general corrosion resistance of zinc coated strip
FR1548017A (de) * 1966-12-27 1968-11-29
DE1558489A1 (de) * 1967-06-15 1970-07-02 Erdmann Jesnitzer Dr Ing Habil Einstufenaetzfaehige Zinklegierungen
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
EP0046458A1 (de) * 1980-08-14 1982-03-03 Th. Goldschmidt AG Verfahren zum Hochtemperaturverzinken

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2197622A (en) * 1937-04-22 1940-04-16 American Rolling Mill Co Process for galvanizing sheet metal
US4389463A (en) * 1981-07-23 1983-06-21 United Technologies Corporation Zinc-aluminum hot dip coated ferrous article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3245765A (en) * 1962-03-08 1966-04-12 Armco Steel Corp Process of improving general corrosion resistance of zinc coated strip
FR1548017A (de) * 1966-12-27 1968-11-29
DE1558489A1 (de) * 1967-06-15 1970-07-02 Erdmann Jesnitzer Dr Ing Habil Einstufenaetzfaehige Zinklegierungen
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
EP0046458A1 (de) * 1980-08-14 1982-03-03 Th. Goldschmidt AG Verfahren zum Hochtemperaturverzinken

Also Published As

Publication number Publication date
US4636354A (en) 1987-01-13
DE3370654D1 (en) 1987-05-07
CA1193154A (fr) 1985-09-10
ES8405849A1 (es) 1984-06-16
ES522090A0 (es) 1984-06-16
ATE26308T1 (de) 1987-04-15
JPS58207363A (ja) 1983-12-02
FR2526445B1 (de) 1984-09-07
FR2526445A1 (fr) 1983-11-10
EP0095402B1 (de) 1987-04-01
US4699815A (en) 1987-10-13
GR79280B (de) 1984-10-22

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