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EP0363784B1 - Flux for hot galvanising - Google Patents

Flux for hot galvanising Download PDF

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Publication number
EP0363784B1
EP0363784B1 EP89118277A EP89118277A EP0363784B1 EP 0363784 B1 EP0363784 B1 EP 0363784B1 EP 89118277 A EP89118277 A EP 89118277A EP 89118277 A EP89118277 A EP 89118277A EP 0363784 B1 EP0363784 B1 EP 0363784B1
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EP
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Prior art keywords
weight
flux
zinc
aluminum
chloride
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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
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EP89118277A
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German (de)
French (fr)
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EP0363784A1 (en
Inventor
Hermann Dr. Meyer
Wilhelm Dr. Goesele
Harry Dr. Parthey
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BASF SE
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BASF SE
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30Fluxes or coverings on molten baths

Definitions

  • the present invention relates to a flux for hot-dip galvanizing, which is particularly suitable for galvanizing with zinc baths containing aluminum.
  • DE-B-2317600 describes a flux solution containing zinc chloride and aluminum chloride and / or hydrogen chloride, which additionally contains corrosion inhibitors known per se and optionally alkali metal chlorides.
  • corrosion inhibitors known per se and optionally alkali metal chlorides.
  • organic compounds in particular organic sulfur compounds, but also butynediol in amounts of from 0.01 to 0.1% by weight are used as corrosion inhibitors.
  • These fluxes are also not suitable for galvanizing with zinc baths that contain a lot of aluminum.
  • fluxes for galvanizing with aluminum-containing zinc baths which are used in the form of aqueous solutions, are described, which consist of 0.3 to 8 wt .-% SnCl2, 1 to 20 wt .-% organic acids such as tartaric acid , Citric acid and maleic acid, or mixtures of organic acids with acid fluorides, and 1 to 20 wt .-% alkali metal chlorides and the rest zinc chloride, exist (see also GB-C-2151259).
  • these fluxes contain acidic fluorides, they are Flux cannot be used for reasons of environmental protection, while fluoride-free fluxes also do not guarantee faultless galvanizing.
  • the object of the present invention was therefore to provide fluxes which can be used in particular for hot-dip galvanizing with zinc baths containing aluminum, which on the one hand lead to perfect galvanizing and on the other hand practically do not react with the aluminum contained in the baths.
  • this object can be achieved with a flux consisting of 70 to 90% by weight zinc chloride 4.5 to 20% by weight potassium chloride 0.4 to 5% by weight of butynediol 0 to 5% by weight of ammonium chloride and 0.1 to 1.5% by weight of a nonionic surfactant of the general formula R1OY x H in the R1 a saturated alkyl radical with 8 to 15 C atoms, or an alkylphenyl radical with 8 to 18 C atoms in the alkyl group, Y is a (-CH2-CH2-O -) - group and x is an integer from 5 to 20 means.
  • the fluxes according to the invention are used in the form of their aqueous solutions in concentrations of 20 to 50% by weight.
  • concentration of the flux depends on the material to be galvanized, whereby higher concentrations are required for thick-walled material. Concentrations of 30 to 45% by weight are preferably used.
  • the nonionic surfactants of the general formula R1OY x H contained in the fluxes according to the invention are ethoxylated alkylphenols or fatty alcohols, the aqueous solution of which is intended to wet the material to be galvanized.
  • the ethoxy group can also be partially replaced by a propoxy group to be replaced.
  • the proportion of the propoxy group should expediently not exceed 30 mol%.
  • the fluxes preferably have a zinc chloride content of 79 to 90% by weight, a potassium chloride content of 10 to 17% by weight, a butynediol content of 1 to 5% by weight and a surfactant content of 0.2 to 1.5% by weight.
  • the presence of ammonium chloride in the flux increases its activity.

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  • 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)
  • Respiratory Apparatuses And Protective Means (AREA)

Abstract

A flux for hot galvanising consists of 70 to 90 % by weight of zinc chloride, 4.5 to 20 % by weight of potassium chloride, 0.4 to 5 % by weight of butynediol, 0 to 5 % by weight of ammonium chloride and 0.1 to 1.5 % by weight of a nonionic surfactant of the general formula R1OYxH, in which R1 is a saturated alkyl radial having 8 to 15 carbon atoms or an alkylphenyl radical having 8 to 18 carbon atoms in the alkyl group, Y is a (-CH2-CH2-O-) group and x is an integer from 5 to 20. The fluxes are suitable for dry galvanising with zinc baths having an aluminium content from 5 to 20 % by weight.

Description

Vorliegende Erfindung betrifft ein Flußmittel für die Feuerverzinkung, das insbesondere für die Verzinkung mit Aluminium enthaltenden Zinkbädern geeignet ist.The present invention relates to a flux for hot-dip galvanizing, which is particularly suitable for galvanizing with zinc baths containing aluminum.

In neuerer Zeit werden in zunehmendem Maße Zinklegierungen für die Verzinkung eingesetzt, die einen Aluminiumgehalt aufweisen, der erheblich über dem bisher üblichen Wert von maximal 0,15 Gew.-% hinausgeht, wobei Aluminiumgehalte von bis zu 20 Gew.-% empfohlen werden (GB-C-2151259). Die Vorteile der bei der Verzinkung mit diesen aluminiumhaltigen Bädern erhaltenen Überzüge liegen in ihrer erhöhten Korrosionsbeständigkeit und ihrer erhöhten mechanischen Festigkeit. Nachteilig ist aber, daß die bisher für aluminiumarme Bäder angewandten Flußmittel zur Erzielung dichter, fehlerfreier Überzüge bei den stärker aluminiumhaltigen Zinkbädern nicht verwendbar sind, da sie häufig zu Fehlverzinkungen führen. Insbesondere bei alkali- und ammoniumchloridhaltigen Flußmitteln, wie sie beispielsweise in der DE-C-2835857 und der DE-C-3115197 beschrieben sind, reagieren die Chloride mit dem in der Zinkschmelze enthaltenem Aluminium zu Aluminiumchlorid. Die Folge ist eine Verarmung des Zinkbades an Aluminium, was erhebliche Kosten wegen des Ersatzes des Aluminiums verursacht und aufwendige Kontrollen des Al-Gehalts erfordert. Gleichzeitig erhöht sich der auf dem Bad schwimmende Ascheanteil, der sorgfältig entfernt werden muß, um Beläge auf dem verzinkten Gut zu vermeiden.More recently, zinc alloys have increasingly been used for galvanizing, which have an aluminum content that significantly exceeds the previously usual maximum of 0.15% by weight, with aluminum contents of up to 20% by weight being recommended (GB -C-2151259). The advantages of the coatings obtained when galvanizing with these aluminum-containing baths are their increased corrosion resistance and their increased mechanical strength. It is disadvantageous, however, that the fluxes used hitherto for low-aluminum baths cannot be used to achieve dense, flawless coatings in the zinc baths which contain more aluminum, since they frequently lead to incorrect galvanizing. Particularly in the case of fluxes containing alkali and ammonium chloride, as described, for example, in DE-C-2835857 and DE-C-3115197, the chlorides react with the aluminum contained in the zinc melt to form aluminum chloride. The result is a depletion of the zinc bath in aluminum, which causes considerable costs due to the replacement of the aluminum and requires extensive controls of the Al content. At the same time, the amount of ash floating on the bath increases, which must be carefully removed in order to avoid deposits on the galvanized material.

In der DE-B-2317600 ist eine Zinkchlorid und Aluminiumchlorid und/oder Chlorwasserstoff enthaltende Flußmittellösung beschrieben, die zusätzlich an sich bekannte Korrosionsinhibitoren und gegebenenfalls Alkalichloride enthält. Als Korrosionsinhibitoren werden neben anorganischen Inhibitoren wie Metallchloriden auch organische Verbindungen, insbesondere organische Schwefelverbindungen, aber auch Butindiol in Mengen von 0,01 bis 0,1 Gew.-% eingesetzt. Auch diese Flußmittel eignen sich nicht für die Verzinkung mit stark aluminiumhaltigen Zinkbädern.DE-B-2317600 describes a flux solution containing zinc chloride and aluminum chloride and / or hydrogen chloride, which additionally contains corrosion inhibitors known per se and optionally alkali metal chlorides. In addition to inorganic inhibitors such as metal chlorides, organic compounds, in particular organic sulfur compounds, but also butynediol in amounts of from 0.01 to 0.1% by weight are used as corrosion inhibitors. These fluxes are also not suitable for galvanizing with zinc baths that contain a lot of aluminum.

In der JA-C-60141858 sind Flußmittel für die Verzinkung mit aluminiumhaltigen Zinkbädern, die in Form wäßriger Lösungen eingesetzt werden, beschrieben, die aus 0,3 bis 8 Gew.-% SnCl₂, 1 bis 20 Gew.-% organischer Säuren wie Weinsäure, Zitronensäure und Maleinsäure, oder Mischungen von organischen Säuren mit sauren Fluoriden, sowie 1 bis 20 Gew.-% Alkalimetallchloriden und Rest Zinkchlorid, bestehen (vgl. auch GB-C-2151259). Für den Fall, daß diese Flußmittel saure Fluoride enthalten, sind solche Flußmittel aus Gründen des Umweltschutzes nicht einsetzbar, während fluoridfreie Flußmittel ebenfalls keine fehlerfreie Verzinkung gewährleisten.In JA-C-60141858 fluxes for galvanizing with aluminum-containing zinc baths, which are used in the form of aqueous solutions, are described, which consist of 0.3 to 8 wt .-% SnCl₂, 1 to 20 wt .-% organic acids such as tartaric acid , Citric acid and maleic acid, or mixtures of organic acids with acid fluorides, and 1 to 20 wt .-% alkali metal chlorides and the rest zinc chloride, exist (see also GB-C-2151259). In the event that these fluxes contain acidic fluorides, they are Flux cannot be used for reasons of environmental protection, while fluoride-free fluxes also do not guarantee faultless galvanizing.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Flußmittel bereitzustellen, die insbesondere für die Feuerverzinkung mit Aluminium enthaltenden Zink-Bädern eingesetzt werden können, die einerseits zu einwandfreien Verzinkungen führen und andererseits praktisch nicht mit dem in den Bädern enthaltenen Aluminium reagieren.The object of the present invention was therefore to provide fluxes which can be used in particular for hot-dip galvanizing with zinc baths containing aluminum, which on the one hand lead to perfect galvanizing and on the other hand practically do not react with the aluminum contained in the baths.

Es wurde gefunden, daß diese Aufgabe mit einem Flußmittel gelöst werden kann, das besteht aus
70 bis 90 Gew.-% Zinkchlorid
4,5 bis 20 Gew.-% Kaliumchlorid
0,4 bis 5 Gew.-% Butindiol
0 bis 5 Gew.% Ammoniumchlorid und
0,1 bis 1,5 Gew.-% eines nichtionischen Tensids der allgemeinen Formel R₁OY x H

Figure imgb0001
in der R₁ einen gesättigten Alkylrest mit 8 bis 15 C-Atomen, oder einen Alkylphenylrest mit 8 bis 18 C-Atomen in der Alkylgruppe, Y eine (-CH₂-CH₂-O-)-Gruppe und x eine ganze Zahl von 5 bis 20 bedeutet.It has been found that this object can be achieved with a flux consisting of
70 to 90% by weight zinc chloride
4.5 to 20% by weight potassium chloride
0.4 to 5% by weight of butynediol
0 to 5% by weight of ammonium chloride and
0.1 to 1.5% by weight of a nonionic surfactant of the general formula R₁OY x H
Figure imgb0001
in the R₁ a saturated alkyl radical with 8 to 15 C atoms, or an alkylphenyl radical with 8 to 18 C atoms in the alkyl group, Y is a (-CH₂-CH₂-O -) - group and x is an integer from 5 to 20 means.

Die erfindungsgemäßen Flußmittel werden in Form ihrer wäßrigen Lösungen in Konzentrationen von 20 bis 50 Gew.-% eingesetzt. Die Konzentration der Flußmittel richtet sich nach dem zu verzinkenden Gut, wobei man höhere Konzentrationen bei dickwandigerem Gut benötigt. Vorzugsweise setzt man Konzentrationen von 30 bis 45 Gew.-% ein.The fluxes according to the invention are used in the form of their aqueous solutions in concentrations of 20 to 50% by weight. The concentration of the flux depends on the material to be galvanized, whereby higher concentrations are required for thick-walled material. Concentrations of 30 to 45% by weight are preferably used.

Bei den in den erfindungsgemäßen Flußmitteln enthaltenen nichtionischen Tensiden der allgemeinen Formel R₁OYxH handelt es sich um ethoxylierte Alkylphenole oder Fettalkohole, deren wäßrige Lösung das Verzinkungsgut benetzen soll. In diesen Tensiden kann die Ethoxygruppe auch teilweise durch eine Propoxygruppe

Figure imgb0002

ersetzt sein. Zweckmäßig sollte der Anteil der Propoxygruppe 30 Mol% nicht übersteigen.The nonionic surfactants of the general formula R₁OY x H contained in the fluxes according to the invention are ethoxylated alkylphenols or fatty alcohols, the aqueous solution of which is intended to wet the material to be galvanized. In these surfactants, the ethoxy group can also be partially replaced by a propoxy group
Figure imgb0002

to be replaced. The proportion of the propoxy group should expediently not exceed 30 mol%.

Als Fettalkohole kommen Alkohole mit 8 bis 15 C-Atomen bzw. als Alkylphenole solche mit einem Alkylrest mit 8 bis 15 C-Atomen in Frage. Die Alkylreste können geradkettig oder verzweigt sein. Die genannten Tenside sind in Wasser klar löslich.Alcohols with 8 to 15 C atoms are suitable as fatty alcohols and those with an alkyl radical with 8 to 15 C atoms are suitable as alkylphenols. The alkyl radicals can be straight-chain or branched. The surfactants mentioned are clearly soluble in water.

Bevorzugt weisen die Flußmittel einen Zinkchloridgehalt von 79 bis 90 Gew.%, einen Kaliumchloridgehalt von 10 bis 17 Gew.%, einen Butindiolgehalt von 1 bis 5 Gew.% und einen Tensidgehalt von 0,2 bis 1,5 Gew.% auf. Durch die Anwesenheit von Ammoniumchlorid im Flußmittel wird dessen Aktivität gesteigert.The fluxes preferably have a zinc chloride content of 79 to 90% by weight, a potassium chloride content of 10 to 17% by weight, a butynediol content of 1 to 5% by weight and a surfactant content of 0.2 to 1.5% by weight. The presence of ammonium chloride in the flux increases its activity.

Die wesentlichen Vorteile der erfindungsgemäßen Flußmittel liegen darin begründet, daß es gelingt einwandfreie Verzinkungen mit aluminiumhaltigen Zinkbädern mit Aluminiumgehalten von 5 bis 20 Gew.% zu erhalten. Weiterhin ist das Flußmittel raucharm, neigt zu geringerer Aschebildung mit den damit verbundenen Verlusten an Zink und Aluminium und es werden darüber hinaus keine umweltbelastende Stoffe emittiert.The main advantages of the fluxes according to the invention lie in the fact that it is possible to achieve perfect galvanizing with aluminum-containing zinc baths with aluminum contents of 5 to 20% by weight. Furthermore, the flux is low in smoke, tends to form less ash with the associated losses of zinc and aluminum and, in addition, no environmentally harmful substances are emitted.

Die in den Beispielen genannten Prozentangaben bedeuten, falls nicht anders vermerkt, Gewichtsprozente.The percentages given in the examples mean percentages by weight, unless stated otherwise.

BeispieleExamples

Ein Eisenstück (50x30x6mm) wird wie üblich entfettet und dann mit Salzsäure behandelt. Nach einer Zwischenspülung mit Wasser wird es in wäßrige Flußmittellösungen eingetaucht, und bei 70°C getrocknet. Anschließend wird es in einem Zinkbad, das 5 % Aluminium enthält bei 480°C verzinkt.A piece of iron (50x30x6mm) is degreased as usual and then treated with hydrochloric acid. After an intermediate rinse with water, it is immersed in aqueous flux solutions and dried at 70.degree. Then it is galvanized in a zinc bath containing 5% aluminum at 480 ° C.

Die Zusammensetzung der (wasserfreien) Flußmittel und die Konzentrationen der Flußmittellösungen sind in der Tabelle wiedergegeben. In der Tabelle bedeutet in der Spalte Tensid (Art)

  • 1) = Isodecanol-oxethylat
    Oxethylierungsgrad 7
  • 2) = Isodecanol-oxethylat
    Oxethylierungsgrad 11
  • 3) = Oxethylierungs/oxpropylierungsprodukt eines C₁₃-C₁₅-Fettalkoholgemisches mit 16 Mol Ethylenoxid und
    4 Mol Propylenoxid/Mol Fettalkohol
  • 4) = Nonylphenol-oxethylat
    Oxethylierungsgrad 14
The composition of the (anhydrous) flux and the concentrations of the flux solutions are shown in the table. In the table in the column surfactant (type) means
  • 1) = isodecanol oxyethylate
    Degree of oxethylation 7
  • 2) = isodecanol oxyethylate
    Degree of oxethylation 11
  • 3) = Oxethylation / oxpropylation product of a C₁₃-C₁₅ fatty alcohol mixture with 16 moles of ethylene oxide and
    4 moles of propylene oxide / mole of fatty alcohol
  • 4) = nonylphenol oxyethylate
    Degree of oxethylation 14

Unter Oxethylierungsgrad werden Mol Ethylenoxid/Mol Fettalkohol bzw. Alkylphenol verstanden.

Figure imgb0003
The degree of oxyethylation means moles of ethylene oxide / moles of fatty alcohol or alkylphenol.
Figure imgb0003

Claims (3)

1. A flux for hot galvanizing, composed of
70-90% by weight of zinc chloride
4.5-20% by weight of potassium chloride
0.4-5% by weight of butynediol
0-5% by weight of ammonium chloride and
0.1-1.5% by weight of a nonionic surfactant of the formula R₁OY x H
Figure imgb0006
where R₁ is saturated alkyl of 8-15 carbons, or alkylphenyl with 8-18 carbons in the alkyl, Y is a (-CH₂-CH₂-O-) group and x is an integer from 5 to 20.
2. A flux as claimed in claim 1, wherein the (-CH₂-CH₂-O-) group is partially replaced by a
Figure imgb0007
group.
3. The use of the flux as claimed in claims 1 and 2 for dry galvanizing with zinc baths with an aluminum content of 0.4-20% by weight.
EP89118277A 1988-10-12 1989-10-03 Flux for hot galvanising Expired - Lifetime EP0363784B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89118277T ATE78879T1 (en) 1988-10-12 1989-10-03 FLUX FOR HOT-DIP GALVANIZING.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3834733 1988-10-12
DE3834733A DE3834733A1 (en) 1988-10-12 1988-10-12 FLUID FOR FIRE GALVANIZATION

Publications (2)

Publication Number Publication Date
EP0363784A1 EP0363784A1 (en) 1990-04-18
EP0363784B1 true EP0363784B1 (en) 1992-07-29

Family

ID=6364947

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89118277A Expired - Lifetime EP0363784B1 (en) 1988-10-12 1989-10-03 Flux for hot galvanising

Country Status (3)

Country Link
EP (1) EP0363784B1 (en)
AT (1) ATE78879T1 (en)
DE (2) DE3834733A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006123945A1 (en) * 2005-05-19 2006-11-23 Fletcher Building Holdings Limited Galvanising procedures
CN103834888A (en) * 2014-03-13 2014-06-04 昆明理工大学 Ammonia-free fluxing agent for hot dipping and use method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH079056B2 (en) * 1990-11-30 1995-02-01 田中亜鉛鍍金株式会社 Flux for hot-dip metal plating by dry flux method and method for producing hot-dip metal plated steel material using this flux
EP2035594A4 (en) * 2006-06-09 2010-12-08 Teck Cominco Metals Ltd High-aluminum alloy for general galvanizing

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE335274A (en) * 1925-08-18 1926-08-31 Tadeusz Liban PROCESS FOR MANUFACTURING MEATLLIC COATINGS
GB1040958A (en) * 1963-07-26 1966-09-01 William Blythe And Company Ltd Improvements in and relating to galvanising fluxes
US3321339A (en) * 1965-05-07 1967-05-23 Du Pont Galvanizing flux
DE2117859C3 (en) * 1971-04-13 1980-01-31 Siemens Ag, 1000 Berlin Und 8000 Muenchen Process for hot-dip tinning or soft soldering of poorly wettable materials
DE2317600C3 (en) * 1973-04-07 1975-08-28 Basf Ag, 6700 Ludwigshafen Aqueous flux solutions for hot-dip galvanizing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006123945A1 (en) * 2005-05-19 2006-11-23 Fletcher Building Holdings Limited Galvanising procedures
CN103834888A (en) * 2014-03-13 2014-06-04 昆明理工大学 Ammonia-free fluxing agent for hot dipping and use method thereof

Also Published As

Publication number Publication date
DE58901945D1 (en) 1992-09-03
EP0363784A1 (en) 1990-04-18
DE3834733A1 (en) 1990-04-19
ATE78879T1 (en) 1992-08-15

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