EP0579642B1 - Verfahren zur feuerverzinkung und legierung zur verwendung der feurverzinkung - Google Patents

Verfahren zur feuerverzinkung und legierung zur verwendung der feurverzinkung Download PDF

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Publication number
EP0579642B1
EP0579642B1 EP92907556A EP92907556A EP0579642B1 EP 0579642 B1 EP0579642 B1 EP 0579642B1 EP 92907556 A EP92907556 A EP 92907556A EP 92907556 A EP92907556 A EP 92907556A EP 0579642 B1 EP0579642 B1 EP 0579642B1
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EP
European Patent Office
Prior art keywords
silicon
zinc
bath
calcium
aluminium
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 - Lifetime
Application number
EP92907556A
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English (en)
French (fr)
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EP0579642A1 (de
Inventor
Richard Bruno Sokolowski
Jean Eugène Lucien Joseph WEGRIA
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.)
Umicore NV SA
Original Assignee
Union Miniere NV SA
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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

Definitions

  • the present invention relates to a method of galvanizing by dipping a series of individual steel objects, according to which a zinc bath containing silicon is used at a concentration which can reach saturation.
  • a zinc bath containing silicon preferably saturated with silicon, is used not only when all the objects to be galvanized have a silicon content of more than 0.02%, but also when at least has objects to be galvanized to such a silicon content, that is to say when it is not excluded that among the objects to be galvanized there are some whose silicon content does not exceed 0.02%, because it has It has been found that galvanizing in such a bath, steels whose silicon content does not exceed 0.02%, leads to very good results which are quite comparable to those obtained with these types of steel in a bath classic.
  • the object of the present invention is to provide a method as defined above, which avoids this drawback.
  • the coating formed on a silicon-free steel immersed for 5 minutes in a conventional bath at 450 ° C has a "conventional" thickness of 66 "m, while one obtains on the same steel and in the same conditions a coating with a thickness of only 37 »m after addition of 0.03% of silicon to the bath.
  • zinc consumption decreases to the same extent as the thickness of the coating.
  • the reduction in thickness is already substantial when 0.005% of silicon is added to the bath.
  • a "conventional" thickness that is to say a thickness of about 70 ⁇ m, has become less and less necessary in many fields of technology. For example, for many applications, automakers would settle for a coating thickness of only about 40 ”m.
  • Part (a) of process of the present invention is therefore particularly advantageous when it is necessary to galvanize a series of steel objects without or with a low silicon content (up to 0.02%) and when one wants to obtain a coating thickness less than 1 'classic thickness, more particularly a thickness less than 50 »m.
  • the minimum silicon content (0.005%) is necessary on the one hand to reinforce the inhibitory effect of aluminum and nickel on the growth of the coating, in particular when the steel to be galvanized contains up to 0.20% of silicon, and on the other hand to avoid the formation in the bath of nickel-iron mattes.
  • the minimum calcium content (0.002%) is necessary to obtain a coating which is free or practically free from defects in the continuity of the coating. It has proven difficult to avoid these defects, even in the presence of calcium, when the aluminum content is greater than 0.06%.
  • a nickel content greater than 0.12% leads to the formation of interfering Ni-Zn compounds. Calcium added above 0.1% plays no role.
  • the galvanizing bath according to part (b) of the process of the present invention is particularly advantageous, not only when one has to galvanize a series of steel objects which all have a silicon content of more than 0.02%, but also when a mixed series must be galvanized, consisting partly of free or low silicon content objects (up to 0.02%) and partially of objects with higher content silicon, and therefore, when a series of steel objects whose composition is unknown is to be galvanized, which is generally the case in custom galvanizing.
  • a galvanizing bath consisting of 0.1% silicon, 0.2% aluminum, 0.1% nickel, 0.1% tin, the rest being zinc.
  • the Applicant has also found that the presence in the bath of at least 0.005% of silicon prevents the formation of bottom mattes (iron-zinc mattes), regardless of the silicon content of the steel to be galvanized, which makes the process of the invention even more attractive.
  • the bath contains in both cases at least 0.01% of silicon, on the one hand to obtain a considerable reduction in the coating thickness, more particularly on steels with 0-0.20% of silicon , and secondly to avoid the formation in the bottom mat bath. It is also desirable that the bath contains in both cases lead at a concentration which can go as far as saturation, for example 0.1 to 1.2%, this in order to reduce the surface tension of the bath. It is further desirable that the bath contains in the first case 0.001-0.015% aluminum and / or 0.002-0.1% calcium, this to protect the zinc against oxidation; otherwise a yellowish film forms on the surface of the bath, which dirty galvanized objects. For the same reason it is advantageous that the nickel bath used in the second case also contains 0.001-0.015% aluminum and / or 0.002-0.1% calcium. The preferential calcium content is 0.005-0.05%.
  • the zinc-based alloy defined above can be used for other applications than that described above.
  • This example concerns the galvanization of a steel having the following composition, in% by weight: 0.050 C, 0.28 Mn, 0.012 Si, 0.009 S, 0.014 P, 0.020 Al, 0.020 Ni, 0.020 Cr and 0.025 Cu.
  • a zinc bath is used and in a second test a zinc bath with 0.029% Si. In both cases the temperature of the bath is 450 ° C and the immersion time 5 minutes.
  • a coating with a thickness of 66 "m is obtained and in the second test, a coating with a thickness of only 39" m.
  • This example concerns the galvanization of a steel having the following composition, in% by weight: 0.144 C, 0.920 Mn, 0.092 Si, 0.010 S, 0.014 P, 0.048 Al, 0.020 Ni, 0.020 Cr, 0.025 Cu.
  • a zinc bath with 0.029% Si is used
  • a zinc bath with 0.10% Ni is used
  • a zinc bath with 0.10% Ni and in a third test a zinc bath with 0.10% Ni and 0.029% of Si.
  • the bath temperature is 450 ° C and the immersion time 5 minutes.
  • the first test we obtain a thickness of more than 200 »m
  • in the second test a thickness of 69» m
  • in the third test a thickness of only 50 »m.

Landscapes

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

Claims (6)

  1. Galvanisationstauchverfahren für eine Serie von einzelnen Gegenständen aus Stahl, gemäß dem man ein Zinkbad verwendet, das Silizium mit einer Konzentration enthält, die bis zur Sättigung gehen kann, dadurch gekennzeichnet, daß
    (a) man entweder die Serie auf eine Weise bildet, daß alle Gegenstände aus einem Stahl sind, der bis zu 0,02% Silizium enthält, und wobei das Zinkbad in diesem ersten Falle zumindest 0,005% Silizium enthält sowie fakultativ eines oder mehrere der folgenden Elemente: Blei mit einer Konzentration, die bis zur Sättigung reichen kann, 0,001-0,015% Aluminium und 0,002-0,1% Kalzium, wobei der Rest Zink und unvermeidbare Unreinheiten sind;
    (b) oder man die Serie so bildet, daß zumindest einer der Gegenstände aus einem Stahl ist, der mehr als 0,02% Silizium enthält und wobei das Zinkbad in diesem zweiten Falle zumindest 0,005% Silizium enthält sowie 0,02-0,06% Aluminium und 0,002-0,1% Kalzium und falcultativ Blei mit einer Konzentration, die bis zur Sättigung reichen kann,
    oder 0,05-0,12% Nickel und fakultativ eines oder mehrere der folgenden Elemente: Blei mit einer Konzentration, die bis zur Sättigung reichen kann, 0,001-0,015% Aluminium und 0,002-0,1% Kalzium, wobei der Rest Zink und unvermeidbare Unreinheiten sind, und wobei die Prozentsätze in Gewicht ausgedrückt sind.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Bad in den beiden Fällen zumindest 0,01% Silizium enthält.
  3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Bad 0,1-1,2% Blei enthält.
  4. Verfahren gemaß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Bad in dem zweiten Fall 0,02-0,06% Aluminium und 0,005-0,05% Kalzium enthält.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Zusammensetzung des Bades im Verlauf des Galvanisationsprozesses beibehält, indem man den Verbrauch des Bades kompensiert, indem man dem Bad hinzufügt:
       entweder eine Legierung auf der Basis von Zink, die enthält
    (a) in dem ersten Fall 0,1-1,5% Silizium und fakultativ eines oder mehrere der folgenden Elemente: 0,1-1,2% Blei, 0,01-0,8% Aluminium und 0,02-1% Kalzium; und
    (b) in dem zweiten Fall 0,1-1,5% Silizum sowie entweder 0,1-0,8% Aluminium und 0,02-1% Kalzium und fakultativ 0,1-1,2% Blei,
    oder
    0,05-0,12% Nickel und fakultativ ein oder mehrere der folgenden Elemente: 0,1-1,2% Blei, 0,01-0,8% Aluminium und 0,02-1% Kalzium, oder
       ein Äquivalent der Legierung basierend auf Zink in der Form von zumindest einer Mutterlegierung und reinem Zink oder in der Form von zumindest einer Mutterlegierung und einer Legierung auf der Basis von Zink, das weniger mit Additiven versetzt ist als die oben genannte Legierung.
  6. Legierungsbarren auf der Basis von Zink, insbesondere zur Verwendung in dem Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß er in Gewichtsanteilen enthält
    entweder 0,1-1,5% Si und 0,02-1% Ca;
    oder 0,1-1,5% Si, 0,01-0,8% Al und 0,02-1% Ca;
    oder 0,1-1,5% Si und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,01-0,8% Al und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,02-1% Ca und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,01-0,8% Al, 0,02-1% Ca und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,1-0,8% Al und 0,02-1% Ca;
    oder 0,1-1,5% Si, 0,1-0,8% Al, 0,02-1% Ca und 0,1-1,2% Pb;
    oder 0,1-1,5% Si und 0,05-0,12% Ni;
    oder 0,1-1,5% Si, 0,05-0,12% Ni und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,05-0,12% Ni und 0,01-0,8% Al;
    oder 0,1-1,5% Si, 0,05-0,12% Ni, 0,01-0,8% Al und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,05-0,12% Ni und 0,02-1% Ca;
    oder 0,1-1,5% Si, 0,05-0,12% Ni, 0,02-1% Ca und 0,1-1,2% Pb;
    oder 0,1-1,5% Si, 0,05-0,12% Ni, 0,01-0,8% Al und 0,02-1% Ca;
    oder 0,1-1,5% Si, 0,05-0,12% Ni, 0,01-0,8% Al, 0,02-1% Ca und 0,1-1,2% Pb;
    wobei der Rest Zink und unvermeidbare Unreinheiten sind.
EP92907556A 1991-04-12 1992-04-02 Verfahren zur feuerverzinkung und legierung zur verwendung der feurverzinkung Expired - Lifetime EP0579642B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9104501 1991-04-12
FR9104501A FR2675159B1 (fr) 1991-04-12 1991-04-12 Procede de galvanisation et alliage de zinc pouvant etre utilise dans ce procede.
PCT/EP1992/000740 WO1992018662A1 (fr) 1991-04-12 1992-04-02 Procede de galvanisation et alliage de zinc pouvant etre utilise dans ce procede

Publications (2)

Publication Number Publication Date
EP0579642A1 EP0579642A1 (de) 1994-01-26
EP0579642B1 true EP0579642B1 (de) 1995-06-28

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ID=9411774

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EP92907556A Expired - Lifetime EP0579642B1 (de) 1991-04-12 1992-04-02 Verfahren zur feuerverzinkung und legierung zur verwendung der feurverzinkung

Country Status (11)

Country Link
EP (1) EP0579642B1 (de)
AU (1) AU1447692A (de)
CA (1) CA2106763A1 (de)
DE (1) DE69203231T2 (de)
FI (1) FI98468C (de)
FR (1) FR2675159B1 (de)
IL (1) IL101384A0 (de)
NO (1) NO933666L (de)
PT (1) PT100376B (de)
TW (1) TW206262B (de)
WO (1) WO1992018662A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110318014A (zh) * 2019-08-16 2019-10-11 四川电力设计咨询有限责任公司 银白色热镀锌镀液及其制备方法和应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010038947A1 (de) * 2010-08-05 2012-02-09 Aktiebolaget Skf Verbindungsanordnung und Verfahren zur Herstellung eines hülsenförmig ausgebildeten Verbindungselements
CN113881911A (zh) * 2021-09-10 2022-01-04 湖南株冶有色金属有限公司 一种热镀锌浴含硅锡合金

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU81061A1 (fr) * 1979-03-19 1980-10-08 Centre Rech Metallurgique Procede de galvanisation
EP0046458A1 (de) * 1980-08-14 1982-03-03 Th. Goldschmidt AG Verfahren zum Hochtemperaturverzinken
DE3734203A1 (de) * 1987-10-09 1989-04-20 Solms Juergen Verfahren zum feuerverzinken von stahlgegenstaenden mit siliciumgehalten ueber 0,02%
DE3911060A1 (de) * 1989-04-06 1990-10-11 Solms Juergen Verfahren zur verringerung des eisengehaltes von zinkschmelzen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110318014A (zh) * 2019-08-16 2019-10-11 四川电力设计咨询有限责任公司 银白色热镀锌镀液及其制备方法和应用
CN110318014B (zh) * 2019-08-16 2020-11-24 四川电力设计咨询有限责任公司 银白色热镀锌镀液及其制备方法和应用

Also Published As

Publication number Publication date
PT100376A (pt) 1993-06-30
FR2675159A1 (fr) 1992-10-16
FI934469A0 (fi) 1993-10-11
TW206262B (de) 1993-05-21
FR2675159B1 (fr) 1993-07-23
PT100376B (pt) 1999-07-30
DE69203231T2 (de) 1996-02-08
DE69203231D1 (de) 1995-08-03
WO1992018662A1 (fr) 1992-10-29
NO933666D0 (no) 1993-10-11
IL101384A0 (en) 1992-11-15
FI98468B (fi) 1997-03-14
EP0579642A1 (de) 1994-01-26
CA2106763A1 (en) 1992-10-13
AU1447692A (en) 1992-11-17
NO933666L (no) 1993-10-12
FI98468C (fi) 1997-06-25
FI934469A (fi) 1993-10-11

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