EP3445889B1 - Verfahren und flussmittel für die feuerverzinkung - Google Patents

Verfahren und flussmittel für die feuerverzinkung Download PDF

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Publication number
EP3445889B1
EP3445889B1 EP17710526.9A EP17710526A EP3445889B1 EP 3445889 B1 EP3445889 B1 EP 3445889B1 EP 17710526 A EP17710526 A EP 17710526A EP 3445889 B1 EP3445889 B1 EP 3445889B1
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Prior art keywords
range
flux
bath
chloride
weight
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EP17710526.9A
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German (de)
English (en)
French (fr)
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EP3445889A1 (de
Inventor
Lars Baumgürtel
Thomas PINGER
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Fontaine Holdings NV
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Fontaine Holdings NV
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Priority to PL17710526T priority Critical patent/PL3445889T3/pl
Priority to EP20151616.8A priority patent/EP3663429A1/de
Priority to SI201730480T priority patent/SI3445889T1/sl
Publication of EP3445889A1 publication Critical patent/EP3445889A1/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
    • C23C2/30—Fluxes or coverings on molten baths
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • 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
    • C23C2/26—After-treatment

Definitions

  • the present invention relates to the technical field of galvanizing iron-based or iron-containing components, in particular steel-based or steel-containing components (steel components), preferably for the automotive or motor vehicle industry, but also for other technical fields of application (e.g. for the construction industry, the area of general mechanical engineering, the electrical industry, etc.) by means of hot-dip galvanizing (hot-dip galvanizing).
  • the present invention relates to a method for hot-dip galvanizing (hot-dip galvanizing) and, moreover, to a flux and flux bath which can be used in this context and their respective use.
  • components made of steel for motor vehicles such as. B. cars, trucks, commercial vehicles etc.
  • other technical areas e.g. construction, mechanical engineering, electronics industry etc.
  • galvanizing it is known to protect steel-based components against corrosion by means of galvanizing (galvanizing).
  • galvanizing the steel is provided with a generally thin layer of zinc to protect the steel from corrosion.
  • Various galvanizing processes can be used to galvanize steel components, i.e. to coat them with a metallic zinc coating, in particular hot-dip galvanizing (also known as hot-dip galvanizing), spray galvanizing (flame spraying with zinc wire), and diffusion galvanizing (Sherard galvanizing) ), galvanizing (electrolytic galvanizing), non-electrolytic galvanizing by means of zinc flake coatings and mechanical galvanizing.
  • hot-dip galvanizing also known as hot-dip galvanizing
  • spray galvanizing flame spraying with zinc wire
  • diffusion galvanizing Stard galvanizing
  • galvanizing electrolytic galvanizing
  • non-electrolytic galvanizing by means of zinc flake coatings and mechanical galvanizing.
  • hot-dip galvanizing The most important method for protecting steel from corrosion by means of metallic zinc coatings is hot-dip galvanizing (hot-dip galvanizing).
  • Steel is immersed continuously (e.g. strip and wire) or piece by piece (e.g. components) at temperatures of around 450 ° C to 600 ° C in a heated boiler with liquid zinc (melting point of zinc: 419.5 ° C), so that a resistant alloy layer of iron and zinc is formed on the steel surface and above that a very firmly adhering pure zinc layer.
  • Hot-dip galvanizing has thus been a method that has been recognized and proven for many years to protect parts or components made of iron materials, in particular steel materials, from corrosion.
  • the typically pre-cleaned or pretreated component is immersed in a hot liquid zinc bath, which causes a reaction with the molten zinc and, as a result, a relatively thin zinc layer metallurgically bonded to the base material.
  • continuous piece galvanizing see e.g. DIN EN ISO 1461
  • continuous strip and wire galvanizing see e.g. DIN EN 10143 and DIN EN 10346.
  • Piece galvanizing as well as strip and wire galvanizing are standardized processes.
  • Continuously galvanized steel strip and continuously galvanized wire are each a preliminary or intermediate product (semi-finished product), which is further processed after galvanizing, in particular by forming, punching, cutting, etc., whereas components to be protected are first completely manufactured and only then hot-dip galvanized (which protects the components from corrosion all around).
  • Bulk galvanizing and strip / wire galvanizing also differ with regard to the zinc layer thickness, which results in different protection periods, depending on the zinc layer.
  • the zinc layer thickness of strip-galvanized sheets is usually at most 20 to 25 micrometers, whereas the zinc layer thickness of galvanized steel parts is usually in the range of 50 to 200 micrometers and even more.
  • Hot-dip galvanizing provides both active and passive corrosion protection. Passive protection is provided by the barrier effect of the zinc coating. Active corrosion protection arises due to the cathodic effect of the zinc coating. Compared to nobler metals of the electrochemical series, such as. As iron, zinc serves as a sacrificial anode, which protects the iron underneath from corrosion until it is completely corroded.
  • the conventional hot-dip galvanizing in particular dip galvanizing, is based in particular on the immersion of iron or steel components in a zinc melt with the formation of a zinc coating or a zinc coating on the surface of the components.
  • a thorough surface preparation of the components to be galvanized is generally required beforehand, which usually involves degreasing with subsequent rinsing, a subsequent acidic pickling with subsequent rinsing and finally a flux treatment (i.e. a so-called fluxing ) with subsequent drying process.
  • the galvanizing of identical or similar components is typically combined or grouped for the entire process (in particular by means of a common product carrier or, for example, a crossbar or frame) a common holding or fastening device for a large number of these identical or similar components).
  • a common product carrier or, for example, a crossbar or frame a common holding or fastening device for a large number of these identical or similar components.
  • a plurality of components on the goods carrier via holding means, such as. B. attached sling, connecting wires or the like.
  • the components are then fed in a grouped state via the product carrier to the individual treatment steps or stages of hot-dip galvanizing.
  • the typical procedure for conventional piece galvanizing using hot-dip galvanizing is usually as follows: First, the component surfaces of the components in question are subjected to degreasing in order to remove residues of fats and oils, it being possible to use aqueous alkaline or acidic degreasing agents as degreasing agents. After cleaning in the degreasing bath, there is usually a rinsing process, typically by immersing it in a water bath, in order to prevent the degreasing agents from being carried over with the galvanized material in the subsequent process step of pickling, in particular when changing from alkaline degreasing to acidic pickling is of great importance.
  • pickling which is used in particular to remove species-specific impurities, such as. B. rust and scale, from the steel surface.
  • the pickling is usually carried out in dilute hydrochloric acid, the duration of the pickling process depending, among other things, on the state of contamination (e.g. degree of rusting) of the galvanized material and the acid concentration and temperature of the pickling bath.
  • a rinsing process is usually carried out after the pickling treatment.
  • fluxing (synonymously also known as flux treatment), whereby the previously degreased and pickled steel surface is treated with a so-called flux, which is typically an aqueous solution of inorganic chlorides, most often with a mixture of zinc chloride (ZnCl 2 ) and ammonium chloride (NH 4 Cl).
  • flux typically an aqueous solution of inorganic chlorides, most often with a mixture of zinc chloride (ZnCl 2 ) and ammonium chloride (NH 4 Cl).
  • the flux is said to increase the wettability between the steel surface and the molten zinc.
  • drying is then usually carried out in order to produce a solid flux film on the steel surface and to remove adhering water, so that undesirable reactions (in particular the formation of water vapor) in the liquid zinc dip bath are subsequently avoided.
  • the components pretreated in the aforementioned manner are then hot-dip galvanized by immersion in the molten zinc melt.
  • the zinc content of the melt according to DIN EN ISO 1461 is at least 98.0% by weight.
  • the galvanized material After immersing the galvanized material in the molten zinc, it remains in the molten zinc bath for a sufficient period of time, in particular until the galvanized material has reached its temperature and is coated with a zinc layer.
  • the surface of the zinc melt is cleaned, in particular, of oxides, zinc ash, flux residues and the like before the galvanized material is then pulled out of the zinc melt again.
  • the hot-dip galvanized component is then subjected to a cooling process (e.g. in the air or in a water bath). Finally, any existing holding means for the component, such as. B. sling, connecting wires or the like, removed.
  • a criterion for the quality of hot-dip galvanizing is the thickness of the zinc coating in ⁇ m (micrometers).
  • the DIN EN ISO 1461 standard specifies the minimum values for the required coating thicknesses, as they are to be supplied for piece galvanizing depending on the material thickness. In practice, the layer thicknesses are significantly higher than the minimum layer thicknesses specified in DIN EN ISO 1461. In general, zinc coatings made by bar galvanizing have a thickness in the range of 50 to 200 micrometers and even more.
  • a coating of differently composed iron / zinc alloy layers is formed.
  • a layer of zinc - also referred to as a pure zinc layer - remains on the top alloy layer, the composition of which corresponds to the zinc melt.
  • a relatively brittle layer based on an alloy is formed between iron and zinc on the steel surface, and only then the pure zinc layer.
  • the relatively brittle iron / zinc alloy layer improves the adhesive strength with the base material, but complicates the formability of the galvanized steel.
  • the zinc melt or the liquid zinc bath add aluminum.
  • a zinc / aluminum alloy with a lower melting temperature compared to pure zinc is produced.
  • hot-dip galvanized components can therefore be easily formed, but still have improved corrosion protection properties - despite the significantly smaller layer thickness compared to conventional hot-dip galvanizing with a quasi aluminum-free zinc melt.
  • a zinc / aluminum alloy used in the hot-dip galvanizing bath has improved fluidity properties compared to pure zinc.
  • zinc coatings which are produced by means of hot-dip galvanizing carried out using such zinc / aluminum alloys have greater corrosion resistance (which is two to six times better than that of pure zinc), better optics, improved formability and better paintability than is formed from pure zinc Zinc coatings. This technology can also be used to produce lead-free zinc coatings.
  • Such a hot-dip galvanizing process using a zinc / aluminum melt or using a zinc / aluminum hot-dip galvanizing bath is known, for example, from US Pat WO 2002/042512 A1 and the relevant document equivalents to this patent family (e.g. EP 1 352 100 B1 , DE 601 24 767 T2 and US 2003/0219543 A1 ).
  • Suitable fluxes for hot-dip galvanizing by means of zinc / aluminum hot-dip baths are also disclosed there, since flux compositions for zinc / aluminum hot-dip galvanizing baths have to be of a different nature than those for conventional hot-dip galvanizing with pure zinc.
  • corrosion protection coatings can be produced with very small layer thicknesses (generally significantly below 50 micrometers and typically in the range from 2 to 20 micrometers) and with very low weight with high cost efficiency, which is why the method described there is commercially available under the name microZINQ ® method is applied.
  • the prior art uses hot-dip galvanizing processes which operate using a zinc / aluminum melt or using a zinc / aluminum hot-dip galvanizing bath (such as WO 2002/042512 A1 ) Flux with significant amounts of lead chloride to allow good wettability in terms of flux treatment, as well as nickel chloride to ensure good temperature resistance of the flux, and possibly also other transition or heavy metal chlorides to achieve other desired properties.
  • the pH value of the flux bath is also generally adjusted in the hot-dip galvanizing processes of the prior art using hydrochloric acid (hydrochloric acid), which under certain circumstances can promote undesirable hydrogen embrittlement of the metal substrate to be treated.
  • the formation of the zinc layer and its properties it has been shown that these can be significantly influenced by alloying elements in the zinc melt.
  • One of the most important elements here is aluminum: It has been shown that even with an aluminum content in the zinc melt of 100 ppm (based on weight), the appearance of the zinc layer can be improved to a lighter, glossier appearance. With increasing aluminum content in the zinc smelt up to 1,000 ppm (weight-based), this effect increases steadily.
  • the disadvantage of using aluminum-alloyed or aluminum-containing zinc melts is the significantly more difficult wettability of the iron or steel surface to be galvanized with the hot liquid Zn / Al melt and the much more sensitive or difficult to handle Reaction between the Zn / Al melt and the iron or steel surface of the component to be treated due to the high affinity of the aluminum for iron.
  • the use of a suitable flux and preheating of the galvanized material is required so that the reaction between the melt and the base material and, along with it, the formation of a homogeneous, closed zinc coating can take place.
  • flux treatment when using aluminum-alloyed or aluminum-containing zinc melts (Zn / Al melts), special fluxes for flux treatment (flux treatment) are required, which often do not always contain ecologically compatible or undesirable heavy metal compounds (usually heavy metal chlorides), especially lead and / or nickel chloride, but possibly also cobalt, manganese, tin, antimony and / or bismuth chloride, which are necessary in order to subsequently guarantee perfect hot-dip galvanizing, in particular without defects on the galvanized components.
  • heavy metal chlorides usually heavy metal chlorides
  • lead and / or nickel chloride but possibly also cobalt, manganese, tin, antimony and / or bismuth chloride, which are necessary in order to subsequently guarantee perfect hot-dip galvanizing, in particular without defects on the galvanized components.
  • the lead chloride is intended in particular to reduce the surface tension and in this way to improve the wettability of the component surface to be treated with the liquid Zn / Al melt, while this Nickel chloride is said to improve the temperature resistance of the flux, in particular with regard to the drying that usually follows the flux treatment.
  • the DE 23 17 600 A1 relates to an aqueous flux solution for hot-dip galvanizing, which contains zinc chloride and optionally alkali chlorides, the flux solution additionally including aluminum chloride and / or hydrogen chloride and optionally a maximum of 4% by weight ammonium chloride, based on the zinc chloride contained in the solution and the alkali chlorides optionally present, and also has known corrosion inhibitors.
  • the EP 1 694 880 A2 an aqueous flux solution for hot-dip galvanizing steel components, the flux solution comprising 200 to 600 g / l zinc chloride and ammonium chloride, the molar ratio between ammonium chloride to zinc chloride being 1.7 to 3.3 and the flux solution 8 g / l to 80 g / l has aluminum chloride.
  • the EP 2 725 115 A1 a flux composition for treating a metallic surface, the flux composition comprising more than 40 and less than 70% by weight zinc chloride, 10 to 30% by weight ammonium chloride, more than 6 and less than 30% by weight of a combination of at least two alkali metal chlorides , including sodium chloride and potassium chloride, 0 to 2% by weight of lead chloride and 0 to 15% by weight of tin chloride.
  • the problem underlying the present invention therefore consists in the provision of a method for hot-dip galvanizing (hot-dip galvanizing), in particular of iron-based or iron-containing components, preferably steel-based or steel-containing components (steel components), using an aluminum-containing or aluminum-alloyed zinc melt and, moreover, an im Flux or flux bath that can be used within the scope of the method, the disadvantages of the prior art described above being at least largely avoided or at least mitigated.
  • such a method or such a flux (bath) is to be provided which, compared to conventional hot-dip galvanizing methods or fluxes (baths) operated using an aluminum-containing or aluminum-alloyed zinc melt, has improved process economy and / or a more efficient, in particular Enables more flexible and / or more reliable, in particular less error-prone process flow and / or improved ecological compatibility.
  • such a method or such a flux is intended to be used without the use of significant amounts of heavy metal compounds, in particular heavy metal chlorides, such as in particular lead and / or nickel chloride, but optionally also other heavy metal chlorides, such as cobalt, manganese, tin, antimony - and / or bismuth chloride, get along as part of the flux treatment and thus have improved ecological compatibility, but still reliably ensure that the treated components are galvanized efficiently and without errors.
  • heavy metal chlorides such as in particular lead and / or nickel chloride
  • other heavy metal chlorides such as cobalt, manganese, tin, antimony - and / or bismuth chloride
  • the present invention proposes - according to a first aspect of the present invention - a method for hot-dip galvanizing according to claim 1; further, in particular special and / or advantageous, configurations of the method according to the invention are the subject of the relevant method subclaims.
  • the present invention relates to a flux bath for the flux treatment of iron or steel components in a hot-dip galvanizing process (hot-dip galvanizing process) according to the independent flux bath claim 6.
  • the present invention relates to a flux composition for the flux treatment of iron or steel components in a hot-dip galvanizing process (hot-dip galvanizing process) according to independent flux composition claim 7.
  • the present invention relates to the use of the flux bath according to the invention or the flux composition according to the invention according to independent use claim 8; further, in particular special and / or advantageous, configurations of the use according to the invention are the subject of the relevant subclaim.
  • the present invention is associated with a large number of completely unexpected advantages, special features and surprising technical effects, the following description of which makes no claim to completeness, but illustrates the inventive character of the present invention:
  • a flux ie a flux bath or a flux composition
  • PbCl 2 lead chloride
  • NiCl 2 nickel chloride
  • the flux used according to the invention in particular the flux composition used according to the invention or the flux bath used according to the invention, at least one aluminum salt and / or at least one silver salt, in particular aluminum chloride (AlCl 3 ) and / or silver chloride (AgCl), preferably aluminum chloride (AlCl 3 ), preferably in very small amounts, which leads to the fact that organic and / or inorganic impurities (such as suspended solids), for example from the upstream treatment steps are still present despite rinsing processes and generally lead to the formation of defects in hot-dip galvanizing, can be discharged or precipitated, so that additional transition metal chlorides can be used to improve the wetting behavior or other properties within the scope of the flux according to the invention s, in particular flux bath or flux composition, can be dispensed with entirely.
  • the efficiency of the method according to the invention can be further improved: As explained in detail below, the time required for drying the flux film due to the alcohol content in the flux bath can be significantly reduced and / or the drying temperatures are significantly reduced. In addition, the filming and wetting with the flux is homogenized in this way.
  • the present invention brings about a significantly improved process economy and a more efficient, in particular more flexible and / or more reliable, in particular less error-prone process sequence and an improved ecological compatibility, in particular due to the omission of lead chloride and nickel chloride, with regard to hot-dip galvanizing by means of aluminum alloys or aluminum-containing zinc melts and possibly further transition or heavy metal chlorides in the flux used, but also the alcohol content in the flux bath.
  • the present invention in particular due to its improved ecological compatibility, can also be used in ecologically sensitive areas in which transition and heavy metal compounds, in particular transition metal and heavy metal chlorides, are to be avoided.
  • the present invention comes without the use of significant amounts of transition and heavy metal compounds, in particular transition and heavy metal chlorides, such as in particular lead and / or nickel chloride, but optionally also other heavy metal chlorides, such as cobalt, manganese, tin, antimony and / or bismuth chloride, as part of the flux treatment, nevertheless reliably ensures that the treated components are galvanized efficiently and without errors.
  • transition and heavy metal compounds such as in particular lead and / or nickel chloride
  • other heavy metal chlorides such as cobalt, manganese, tin, antimony and / or bismuth chloride
  • the peculiarities of the process according to the invention are also immediately apparent in the process products available, ie H. the hot-dip galvanized or hot-dip galvanized iron and steel components: These not only have improved mechanical and optical properties and improved corrosion protection properties, but are also completely free of defects, and this with relatively small layer thicknesses in relation to the hot-dip galvanizing layer. In addition, no undesired transition metal or heavy metals can be introduced from the flux into the ultimately hot-dip galvanizing layer, since transition metal or heavy metals are completely avoided in the course of the flux treatment according to the present invention.
  • Transition metal or heavy metals are at best added or alloyed to the zinc melt or the hot-dip galvanizing bath in order to specifically adjust certain properties of the hot-dip galvanizing layer, but then in an ecologically compatible manner, since these are an integral part of the hot-dip galvanizing layer and are incorporated therein as a fixed alloy component or are involved.
  • the zinc chloride ensures very good coverage of the iron or steel surface, in particular because of the flat formation of the dried ZnCl 2 crystals. However, since 100% coverage is practically impossible to achieve and smaller oxidation points or If there is always a thin layer of oxidation, a sufficient amount of ammonium chloride is added to the flux composition, which is deposited on the component surface and thermally decomposes to NH 3 and HCl when it is immersed in the zinc melt, so that the last oxide residues from the component surface be removed.
  • alkali and / or alkaline earth salts in particular NaCl and / or KCl, are added which raise the melting point of the flux composition and thus enable high and effective drying.
  • the alcohol content can shorten the time required to dry the flux film, especially due to the lower evaporation point of alcohol compared to water. This leads to a noteworthy improvement compared to the prior art, in which the galvanizing cycle defines the maximum drying time and, as a result, often, especially in the case of solid components, the drying time is not sufficient to dry the flux film sufficiently.
  • a completely dried flux film enables a clean reaction with the zinc melt without spills due to evaporating residual water.
  • better drying results in less zinc ash accumulation, which reduces the risk of zinc ash buildup on the galvanized material (i.e. better galvanizing quality and less reworking).
  • faster drying means that the drying time and / or the drying temperature can be reduced, which in turn means an energy saving and / or an increase in productivity.
  • the flux in the zinc bath also burns off more quickly (also due to the lower evaporation point). H. the energy of the zinc melt can flow directly into the heating of the component, which in turn leads to a faster and more effective galvanizing process.
  • the proportion of alcohol used is particularly dependent on the aluminum content of the zinc melt used, on the required drying or preheating (which in turn depends on the component geometry, in particular the material thickness, thicker components requiring longer drying times, on the zinc alloy used and on the thickness of the applied flux film, whereby thicker flux layers, depending on the salt concentration, pull-out speed, roughness of the steel surface, etc., require longer drying times), the degree of contamination of the galvanized material and the technical requirements (e.g. performance of the drying oven, clocking of the galvanizing process, suction power on Flux bath etc.).
  • the method according to the invention comprises the method steps (a) to (g) described above.
  • Process steps (a) to (d) can in principle be carried out in a manner known per se to the person skilled in the art. In principle, this also applies to the basic implementation of the other process steps, in particular also with regard to process step (e) of the flux treatment.
  • the flux bath is usually acidified in the course of process step (e).
  • the flux bath is set to a defined and / or predetermined, in particular acidic pH, in particular in the pH range from 0 to 6.9, preferably in the pH range from 0.5 to 6, 5, preferably in the pH range from 1 to 5.5, particularly preferably in the pH range from 1.5 to 5, very particularly preferably in the pH range from 2 to 4.5, even more preferably in the pH range from 2 to 4.
  • the flux bath is adjusted to a defined and / or predetermined, in particular acidic pH, the adjustment of the pH using a preferably inorganic acid in combination with a preferably inorganic basic compound, in particular ammonia (NH 3 ) , he follows.
  • a preferably inorganic acid in combination with a preferably inorganic basic compound, in particular ammonia (NH 3 )
  • NH 3 ammonia
  • the weight-related alcohol / water ratio can vary within wide ranges.
  • the flux bath contains the alcohol / water mixture in a weight-based alcohol / water ratio in the range from 0.5: 99.5 to 99: 1, in particular in the range from 2: 98 to 95: 5, preferably in the range from 5:95 to 90:10, preferably in the range from 5:95 to 50:50, particularly preferably in the range from 5:95 to 45:55, very particularly preferably in the range from 5:95 to 50:50, even more preferably in the range from 10:90 to 30:70, based on the alcohol / water mixture.
  • the flux bath contains the alcohol, based on the alcohol / water mixture, in an amount of at least 0.5% by weight, in particular in an amount of at least 1% by weight, preferably in an amount of at least 2% by weight, particularly preferably in an amount of at least 3% by weight, even more preferably in an amount of at least 4% by weight.
  • the flux bath usually contains the alcohol, based on the alcohol / water mixture, in an amount of up to 90% by weight, in particular in an amount of up to 70% by weight, preferably in an amount of up to 50% by weight .-%, particularly preferably in an amount of up to 30 wt .-%, even more preferably in an amount of up to 25 wt .-%.
  • the alcohol of the alcohol / water mixture of the flux bath is selected from alcohols with boiling points under atmospheric pressure (1,013.25 hPa) in the range from 40 ° C to 200 ° C, in particular in the range from 45 ° C to 180 ° C, preferably in the range from 50 ° C to 150 ° C, particularly preferably in the range from 55 ° C to 130 ° C, very particularly preferably in the range from 60 ° C to 110 ° C.
  • the alcohol in the alcohol / water mixture of the flux bath is a water-miscible and / or a water-soluble alcohol.
  • the alcohol of the alcohol / water mixture of the flux bath is advantageously an alcohol which forms an azeotropic mixture with water.
  • the alcohol of the alcohol / water mixture of the flux bath is selected from the group of monohydric C 1 -C 4 alcohols and their mixtures.
  • the alcohol of the alcohol / water mixture of the flux bath is selected from the group of linear or branched, saturated, aliphatic, primary, secondary or tertiary monohydric C 1 -C 4 alcohols and mixtures thereof.
  • the alcohol of the alcohol / water mixture in the flux bath is selected from the group consisting of methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol and their Mixtures.
  • the flux bath can - in addition to the ingredients or components mentioned above - also at least one wetting agent and / or surfactant, in particular at least one ionic or nonionic wetting agent and / or surfactant, preferably at least one nonionic wetting agent and / or Surfactant.
  • the flux bath can contain the at least one wetting agent and / or surfactant in amounts of 0.0001 to 15% by weight, preferably in amounts of 0.001 to 10% by weight, preferably in amounts of 0.01 to 8% by weight. , more preferably in quantities of 0.01 to 6% by weight, very particularly preferably in quantities of 0.05 to 3% by weight, still more preferably in quantities of 0.1 to 2% by weight on the flux bath.
  • the flux can contain the at least one wetting agent and / or surfactant, in particular in amounts of 0.0001 to 10% by volume, preferably in amounts of 0.001 to 8% by volume, preferably in amounts of 0.01 to 5% by volume. %, more preferably in amounts of 0.01 to 5% by volume, very particularly preferably in amounts of 0.05 to 3% by volume, even more preferably in amounts of 0.1 to 2% by volume, based on the flux bath.
  • the amount or concentration of the flux composition used according to the invention in the flux bath used according to the invention can likewise vary within wide ranges:
  • the flux bath can contain the flux composition in an amount of at least 150 g / l, in particular in an amount of at least 200 g / l, preferably in an amount of at least 250 g / l, preferably in an amount of at least 300 g / l preferably in an amount of at least 400 g / l, very particularly preferably in an amount of at least 450 g / l, even more preferably in an amount of at least 500 g / l, in particular calculated as the total salt content of the flux composition.
  • the flux bath can preferably contain the flux composition in an amount of 150 g / l to 750 g / l, in particular in an amount of 200 g / l to 700 g / l, preferably in an amount of 250 g / l to 650 g / l. preferably in an amount of 300 g / l to 625 g / l, particularly preferably in an amount of 400 g / l to 600 g / l, very particularly preferably in an amount of 450 g / l to 580 g / l, even more preferably contained in an amount of 500 g / l to 575 g / l, in particular calculated as the total salt content of the flux composition.
  • the flux composition used according to the invention can contain an alkali and / or alkaline earth chloride as the alkali and / or alkaline earth salt of component (iii).
  • the flux composition used according to the invention as the alkali and / or alkaline earth salt of component (iii) can be at least one alkali and / or alkaline earth salt of an alkali and / or alkaline earth metal from the group of lithium (Li), sodium (Na), potassium (K ), Rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) as well as the combinations.
  • the flux composition used according to the invention as the alkali and / or alkaline earth salt of component (iii) comprises at least two different alkali and / or alkaline earth salts, in particular at least two alkali and / or alkaline earth salts of an alkali and / or alkaline earth metal the group of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium ( Ba) and the combinations.
  • the flux composition used according to the invention as the alkali and / or alkaline earth metal salt of component (iii) comprises at least two different alkali metal salts, in particular two different alkali metal chlorides, preferably sodium chloride and potassium chloride, in particular with a sodium / potassium weight ratio in the range from 50: 1 to 1:50, in particular in the range from 25: 1 to 1:25, preferably in the range from 10: 1 to 1:10.
  • the flux composition used according to the invention is at least substantially free, preferably completely free, also of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride (SbCl 3 ) is trained.
  • CoCl 2 cobalt chloride
  • MnCl 2 manganese chloride
  • SnCl 2 tin chloride
  • BiCl 3 bismuth chloride
  • SbCl 3 antimony chloride
  • the flux composition used according to the invention is at least substantially free, preferably completely free, of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride (SbCl 3 ). and / or if the flux composition is at least substantially free, preferably completely free, of chlorides from the group of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride (SbCl 3 ) is formed.
  • the flux composition used according to the invention is at least substantially free, preferably completely free, of salts and compounds of metals from the group of lead (Pb), nickel (Ni), cobalt (Co), manganese (Mn) , Tin (Sn), bismuth (Bi) and antimony (Sb) is formed.
  • the flux composition used according to the invention apart from zinc chloride (ZnCl 2 ) and aluminum and / or silver salt, in particular silver chloride (AgCl) and / or aluminum chloride (AlCl 3 ), is at least essentially free, preferably completely free of salts and compounds of transition and heavy metals.
  • the procedure is generally such that the flux treatment in process step (e) by contacting the iron or steel component with the flux bath and / or the flux composition, in particular by dipping or spray application, preferably dipping, he follows. It is particularly advantageous if the iron or steel component is used for a duration of 0.001 to 30 minutes, in particular 0.01 to 20 minutes, preferably 0.1 to 15 minutes, preferably 0.5 to 10 minutes, particularly preferably 1 to 5 minutes, is brought into contact with the flux bath and / or the flux composition, in particular immersed in the flux bath.
  • the iron or steel component can be used for up to 30 minutes, in particular up to 20 minutes, preferably up to 15 minutes, preferably up to 10 minutes, particularly preferably up to 5 minutes, with the flux bath and / or the flux composition in Contacted, especially immersed in the flux bath.
  • the drying treatment in process step (f) of the process according to the invention it is preferred according to the invention if the drying treatment in process step (f) at a temperature in the range from 50 to 400 ° C., in particular in the range from 75 to 350 ° C., is preferred in the range from 100 to 300 ° C., preferably in the range from 125 to 275 ° C., particularly preferably in the range from 150 to 250 ° C., and / or when the drying treatment in process step (f) takes place at a temperature of up to 400 ° C. , in particular up to 350 ° C, preferably up to 300 ° C, preferably up to 275 ° C, particularly preferably up to 250 ° C.
  • the procedure is such that the drying treatment in process step (f) is carried out in such a way that the surface of the iron or steel component during drying has a temperature in the range from 100 to 300 ° C., in particular in the range from 125 to 275 ° C. preferably in the range from 150 to 250 ° C, preferably in the range from 160 to 225 ° C, particularly preferably in the range from 170 to 200 ° C.
  • the drying treatment in process step (f) can typically be carried out in the presence of and / or by means of air.
  • the drying treatment can take place in at least one drying device, in particular in at least one oven.
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath contain an amount of aluminum in the range from 0.0001 to 25% by weight.
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath can contain a quantity Zinc of at least 75% by weight, in particular at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, and optionally at least one further metal, in particular in amounts of up to 5% by weight % and / or in particular selected from the group of bismuth (Bi), lead (Pb), tin (Sn), nickel (Ni), silicon (Si), magnesium (Mg) and combinations thereof. All of the quantities mentioned above should be selected such that a total of 100% by weight results.
  • the zinc melt used contains other alloy components or alloy metals in addition to aluminum, this can be used to control the process control in a targeted manner: the presence of lead and bismuth in particular can reduce the surface tension and thus improve the wettability of the surface to be galvanized, while the In the presence of tin, the optical properties, in particular the gloss, of the resulting galvanizing layer can be improved, the layer thicknesses can be reduced further by the presence of nickel, the service life of the zinc bath container (e.g. steel kettle) can be extended by the presence of silicon and by the presence of magnesium the corrosion properties, especially the corrosion resistance, of the resulting galvanizing layer can be improved.
  • the zinc bath container e.g. steel kettle
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath can have a temperature in the range from 375 ° C. to 750 ° C., in particular temperature in the range from 380 ° C. to 700 ° C. , preferably temperature in the range from 390 ° C to 680 ° C, more preferably in the range from 395 ° C to 675 ° C.
  • the hot-dip galvanizing step (g) is typically carried out in such a way that the iron or steel component is immersed, in particular immersed and moved, in the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or in the galvanizing bath, in particular for a period of time which is sufficient to ensure effective hot-dip galvanizing (hot-dip galvanizing), in particular for a period in the range from 0.0001 to 60 minutes, preferably in the range from 0.001 to 45 minutes, preferably in the range from 0.01 to 30 minutes, more preferably in the range of 0.1 to 15 minutes.
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath can be contacted and / or flushed or passed through with at least one inert gas, in particular nitrogen.
  • the method according to the invention can be operated continuously or discontinuously.
  • the iron or steel component to be treated can be a single product or a large number of individual products. In this case, a discontinuous procedure is preferred, although a continuous procedure is generally not excluded.
  • the iron or steel component can also be a long product, in particular a wire, tube, sheet metal, coil material or the like.
  • a continuous procedure is preferred, although a discontinuous procedure is also not excluded in this regard.
  • the hot-dip galvanizing (hot-dip galvanizing) carried out in method step (g) can be followed by a cooling step (h), i. H. the hot-dip galvanized (hot-dip galvanized) iron or steel component in process step (g) can be subjected to a cooling treatment (h), optionally followed by a further post-processing and / or post-treatment step (i).
  • the optional cooling step (h) and / or the optional cooling treatment (h) can be carried out in particular by means of air and / or in the presence of air, preferably to ambient temperature.
  • the flux bath of the flux treatment device (E) is usually acidic.
  • the flux bath is set to a defined and / or predetermined, in particular acidic pH, in particular in the pH range from 0 to 6.9, preferably in the pH range from 0.5 to 6.5, preferably in the pH range from 1 to 5.5, particularly preferably in the pH range from 1.5 to 5, very particularly preferably in the pH range from 2 to 4.5, even more preferably in the pH range Value range from 2 to 4.
  • the flux bath is set to a defined and / or predetermined, in particular acidic pH, the pH being set by means of a preferably inorganic acid in combination with a preferably inorganic basic compound, in particular ammonia (NH 3 ) , is done.
  • a defined and / or predetermined, in particular acidic pH the pH being set by means of a preferably inorganic acid in combination with a preferably inorganic basic compound, in particular ammonia (NH 3 ) , is done.
  • the flux bath used in the flux treatment device (E) its composition can vary within wide ranges:
  • the system is typically designed such that the flux bath contains the alcohol / water mixture in a weight-based alcohol / water ratio in the range from 0.5: 99.5 to 99: 1, in particular in the range from 2: 98 to 95: 5 , preferably in the range from 5:95 to 90:10, preferably in the range from 5:95 to 50:50, particularly preferably in the range from 5:95 to 45:55, very particularly preferably in the range from 5:95 to 50: 50, more preferably in the range from 10:90 to 30:70, based on the alcohol / water mixture.
  • the system is usually designed in such a way that the flux bath contains the alcohol, based on the alcohol / water mixture, in an amount of at least 0.5% by weight, in particular in an amount of at least 1% by weight, preferably in one Contains an amount of at least 2% by weight, particularly preferably in an amount of at least 3% by weight, even more preferably in an amount of at least 4% by weight.
  • the system is usually designed in such a way that the flux bath contains the alcohol, based on the alcohol / water mixture, in an amount of up to 90% by weight, in particular in an amount of up to 70% by weight, preferably in one Contains up to 50 wt .-%, particularly preferably in an amount of up to 30 wt .-%, more preferably in an amount of up to 25 wt .-%.
  • the flux treatment device (E) is designed in such a way that the alcohol of the alcohol / water mixture of the flux bath is selected from alcohols with boiling points under atmospheric pressure (1,013.25 hPa) in the range from 40 ° C to 200 ° C , in particular in the range from 45 ° C to 180 ° C, preferably in the range from 50 ° C to 150 ° C, particularly preferably in the range from 55 ° C to 130 ° C, very particularly preferably in the range from 60 ° C to 110 ° C.
  • alcohols with boiling points under atmospheric pressure (1,013.25 hPa) in the range from 40 ° C to 200 ° C , in particular in the range from 45 ° C to 180 ° C, preferably in the range from 50 ° C to 150 ° C, particularly preferably in the range from 55 ° C to 130 ° C, very particularly preferably in the range from 60 ° C to 110 ° C.
  • the alcohol of the alcohol / water mixture of the flux bath is a water-miscible and / or a water-soluble alcohol.
  • the alcohol of the alcohol / water mixture of the flux bath is an alcohol which forms an azeotropic mixture with water.
  • the alcohol of the alcohol / water mixture of the flux bath is selected from the group of linear or branched, saturated, aliphatic, primary, secondary or tertiary monohydric C 1 -C 4 alcohols and mixtures thereof.
  • the system is designed such that the alcohol in the alcohol / water mixture in the flux bath is selected from the group consisting of methanol, ethanol, propan-1-ol, propan-2-ol, butan-1- ol, butan-2-ol and mixtures thereof.
  • the flux bath also contains at least one wetting agent and / or surfactant, in particular at least one ionic or nonionic wetting agent and / or surfactant, preferably at least one nonionic wetting agent and / or surfactant .
  • the amounts of wetting agent and / or surfactant in the flux bath used according to the invention can vary within a wide range:
  • the flux bath can contain the at least one wetting agent and / or surfactant in amounts of 0.0001 to 15% by weight, preferably in amounts of 0.001 to 10% by weight, preferably in amounts of 0.01 to 8% by weight. , more preferably in quantities of 0.01 to 6% by weight, very particularly preferably in quantities of 0.05 to 3% by weight, still more preferably in quantities of 0.1 to 2% by weight on the flux bath.
  • the flux bath can contain the at least one wetting agent and / or surfactant in amounts of 0.0001 to 10% by volume, preferably in amounts of 0.001 to 8% by volume, preferably in amounts of 0.01 to 5% by volume , more preferably in quantities of 0.01 to 5% by volume, very particularly preferably in quantities of 0.05 to 3% by volume, even more preferably in quantities of 0.1 to 2% by volume on the flux bath.
  • the amount or concentration of the flux composition used according to the invention in the flux bath designed according to the invention can likewise vary within wide ranges:
  • the flux bath contains the flux composition in an amount of at least 150 g /, in particular in an amount of at least 200 g / l, preferably in an amount of at least 250 g / l, preferably in an amount of at least 300 g / l, particularly preferably in an amount of at least 400 g / l, very particularly preferably in an amount of at least 450 g / l, even more preferably in an amount of at least 500 g / l, in particular calculated as the total salt content of the flux composition.
  • the flux bath contains the flux composition in an amount of 150 g / l to 750 g / l, in particular in an amount of 200 g / l to 700 g / l, preferably in an amount of 250 g / l up to 650 g / l, preferably in an amount of 300 g / l to 625 g / l, particularly preferably in an amount of 400 g / l to 600 g / l, very particularly preferably in an amount of 450 g / l to 580 g / l, more preferably in an amount of 500 g / l to 575 g / l, contains, in particular calculated as the total salt content of the flux composition.
  • component (iii) of the flux composition used according to the invention can also vary within wide ranges: It is preferred according to the invention if the flux composition contains an alkali and / or alkaline earth chloride as the alkali and / or alkaline earth salt of component (iii).
  • the flux composition used according to the invention as the alkali and / or alkaline earth salt of component (iii) can be at least one alkali and / or alkaline earth salt of an alkali and / or alkaline earth metal from the group of lithium (Li), sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs), Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr) and Barium (Ba) as well as the combinations.
  • the flux composition used according to the invention as the alkali and / or alkaline earth salt of component (iii) can contain at least two different alkali and / or alkaline earth salts, in particular at least two alkali and / or alkaline earth salts of an alkali and / or alkaline earth metal from the group of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) and the combinations.
  • lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) and the combinations.
  • the flux composition used according to the invention in accordance with another typical embodiment as the alkali and / or alkaline earth salt of component (iii), can contain at least two different alkali salts, in particular two different alkali metal chlorides, preferably sodium chloride and potassium chloride, in particular with a sodium / potassium weight ratio in the range from 50: 1 to 1:50, in particular in the range from 25: 1 to 1:25, preferably in the range from 10: 1 to 1:10.
  • the flux composition used according to the invention is at least substantially free, preferably completely free, also of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride (SbCl 3 ). is trained.
  • the flux composition used according to the invention is at least substantially free, preferably completely free, of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride (SbCl 3 ) and / or if the flux composition is at least substantially free, preferably completely free, of chlorides from the group of cobalt chloride (CoCl 2 ), manganese chloride (MnCl 2 ), tin chloride (SnCl 2 ), bismuth chloride (BiCl 3 ) and antimony chloride ( SbCl 3 ) is formed.
  • the flux composition used according to the invention is at least substantially free, preferably completely free, of salts and compounds of metals from the group of lead (Pb), nickel (Ni), cobalt (Co), manganese (Mn), Tin (Sn), bismuth (Bi) and antimony (Sb) is formed.
  • the flux composition apart from zinc chloride (ZnCl 2 ) and aluminum and / or silver salt, in particular silver chloride (AgCl) and / or aluminum chloride (AlCl 3 ), is at least essentially free, preferably completely free , of salts and compounds of transition and heavy metals.
  • the flux treatment device (E) comprises a device for bringing the iron or steel component into contact with the flux bath and / or the flux composition, in particular a device for dipping or for spray application, preferably a device for dipping.
  • the device for bringing the iron or steel component into contact with the flux bath and / or the flux composition can be controlled and / or controlled in such a way, in particular by means of a control device, that the iron or steel component lasts for a period of 0.001 to 30 minutes, in particular 0.01 to 20 minutes, preferably 0.1 to 15 minutes, preferably 0.5 to 10 minutes, particularly preferably 1 to 5 minutes, with the flux bath and / or the flux composition is brought into contact, in particular immersed in the flux bath.
  • the device for bringing the iron or steel component into contact with the flux bath and / or the flux composition can be controlled and / or controlled in such a way, in particular by means of a control device, that the iron or steel component lasts for a period of time of up to 30 minutes, in particular up to 20 minutes, preferably up to 15 minutes, preferably up to 10 minutes, particularly preferably up to 5 minutes, is brought into contact with the flux bath and / or the flux composition, in particular is immersed in the flux bath .
  • the drying treatment device (F) can be controlled and / or controlled in such a way, in particular by means of a control device, that the drying treatment at a temperature in the range from 50 to 400 ° C., in particular in the range from 75 to 350 ° C, preferably in the range from 100 to 300 ° C, preferably in the range from 125 to 275 ° C, particularly preferably in the range from 150 to 250 ° C, and / or that the drying treatment in process step (f) takes place at a temperature up to to 400 ° C, in particular up to 350 ° C, preferably up to 300 ° C, preferably up to 275 ° C, particularly preferably up to 250 ° C.
  • the drying treatment device (F) can be controlled and / or controlled in this way, in particular by means of a control device, that the drying treatment is carried out in such a way that the surface of the iron or steel component has a temperature in the range during drying from 100 to 300 ° C, in particular in the range from 125 to 275 ° C, preferably in the range from 150 to 250 ° C, preferably in the range from 160 to 225 ° C, particularly preferably in the range from 170 to 200 ° C.
  • the drying treatment is typically carried out in the presence of air.
  • the drying treatment device (F) can have at least one inlet for introducing and / or introducing air.
  • the drying treatment device (F) usually comprises at least one drying device, in particular at least one oven.
  • the hot-dip galvanizing device (G) of the plant comprises at least one aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”), in particular at least one galvanizing bath containing aluminum-containing, in particular aluminum-alloyed zinc melt, preferably designed for dipping iron or steel components.
  • Zn / Al melt aluminum-containing, in particular aluminum-alloyed zinc melt
  • the system suitable for carrying out the method according to the invention is typically designed such that the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath, an amount of aluminum in the range from 0.0001 to 25 % By weight, in particular in the range from 0.001 to 20% by weight, preferably in the range from 0.005 to 17.5% by weight, preferably in the range from 0.01 to 15% by weight, particularly preferably in the range from 0.02 to 12.5 wt .-%, very particularly preferably in the range of 0.05 to 10 wt .-%, even more preferably in the range of 0.1 to 8 wt .-%, based on the aluminum-containing , in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath, in particular the aluminum-containing one.
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath in particular the aluminum-containing one.
  • the aluminum-alloyed zinc melt (“Zn / Al-melt”) and / or the galvanizing bath can contain at least an amount of zinc 75% by weight, in particular at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, and optionally at least one further metal, in particular in amounts of up to 5% by weight and / or in particular selected from the group of bismuth (Bi), lead (Pb), tin (Sn), nickel (Ni), silicon (Si), magnesium (Mg) and combinations thereof. All of the quantities mentioned above should be selected such that a total of 100% by weight results.
  • the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath can have a temperature in the range from 375 ° C. to 750 ° C., in particular temperature in the range from 380 ° C. to 700 ° C, preferably temperature in the range from 390 ° C to 680 ° C, more preferably in the range from 395 ° C to 675 ° C.
  • the system suitable for carrying out the method according to the invention is designed such that the hot-dip galvanizing device (G) is designed and / or operable in such a way and / or is designed and / or operated in this way, in particular is controllable and / or is controlled in this way, in particular by means of a control device that the iron or steel component is immersed in the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or in the galvanizing bath, in particular immersed and moved therein, in particular for a period of time which is sufficient, to ensure effective hot-dip galvanizing (hot-dip galvanizing), in particular for a period in the range from 0.0001 to 60 minutes, preferably in the range from 0.001 to 45 minutes, preferably in the range from 0.01 to 30 minutes, more preferably in the range from 0.1 to 15 minutes.
  • the hot-dip galvanizing device is designed and / or operable in such a way and / or is designed and / or operated in this way,
  • the hot-dip galvanizing device (G) has at least one device for contacting and / or rinsing or passing through the aluminum-containing, in particular aluminum-alloyed zinc melt (“Zn / Al melt”) and / or the galvanizing bath has at least one inert gas, in particular nitrogen.
  • the system suitable for carrying out the method according to the invention can in principle be designed to be operated continuously or discontinuously, or it can be operated continuously or discontinuously.
  • the installation suitable for carrying out the method according to the invention can be designed in such a way that the iron or steel component can be hot-dip galvanized as a single product or as a large number of individual products or that the iron or steel component as a long product, in particular a wire, tube , Sheet metal, coil material or the like, is hot-dip galvanized.
  • the system suitable for carrying out the method according to the invention downstream in the process direction or downstream of the hot-dip galvanizing device (F), also has at least cooling device (H) for cooling the hot-dip galvanized iron or steel component in the hot-dip galvanizing device (F).
  • the cooling device (H) can be designed and / or operated in the presence of air.
  • the system according to the invention, downstream in the process direction or downstream of the optional cooling device (H), can also have at least one post-processing and / or post-treatment device (I) for post-processing and / or post-treatment of the hot-dip galvanized and cooled iron or steel component.
  • the flux composition according to the invention is dissolved or dispersed, preferably dissolved, in a liquid phase of a flux bath, the liquid phase of the flux bath comprising an alcohol / water mixture.
  • Yet another object of the present invention - according to a fourth or fifth aspect of the present invention - is the use of the flux bath according to the invention described above or the flux composition according to the invention described above for the flux treatment of iron or steel components in a hot-dip galvanizing process (hot dip galvanizing process).
  • the flux composition is combined with a flux bath, the flux bath comprising a liquid phase containing an alcohol / water mixture, the liquid phase of the flux bath containing the flux composition, in particular in dissolved or dispersed form , preferably in dissolved form.
  • a hot-dip galvanized (hot-dip galvanized) iron or steel component can be obtained by a method according to the invention, as described above, or in a plant suitable for carrying out the method according to the invention, as described above.
  • the products according to the invention have particular advantages, in particular a reduced transition or heavy metal content as well as improved mechanical properties and corrosion protection properties.
  • the hot-dip galvanized iron or steel component obtainable by the process according to the invention, it is preferred if this has a hot-dip galvanizing layer on its surface with a thickness of 0.5 to 300 ⁇ m, in particular 1 to 200 ⁇ m, preferably 1.5 to 100 ⁇ m Thickness, preferably 2 to 30 microns, is provided.
  • this hot-dip galvanized iron or steel component is provided on its surface with a hot-dip galvanizing layer, the hot-dip galvanizing layer being at least substantially free, preferably completely free, of lead (Pb) and / or nickel (Ni) from the flux treatment.
  • the hot-dip galvanized iron or steel component obtainable by the method according to the invention is provided with a hot-dip galvanizing layer on its surface, the hot-dip galvanizing layer being at least essentially free, preferably completely free, of heavy metals from the group of lead originating from the flux treatment (Pb), nickel (Ni), cobalt (Co), manganese (Mn), tin (Sn), bismuth (Bi) and antimony (Sb).
  • FIG. 1 The process flow diagram shown schematically shows the successive process steps or process steps a) to i), the process steps b), d), f), h) and i), in particular process steps h) and i), being optional.
  • FIG. 1 The diagram shows the process flow as follows, the method according to the invention successively comprising the steps mentioned below in this order: degreasing (step a)), rinsing (step b), optional), pickling (step c)), rinsing (step d) , optional), flux bath treatment (step e)), drying (step f), optional), hot-dip galvanizing (step g)), cooling (step h), optional) and post-processing or post-treatment (step i), optional).
  • Fig. 2 the system suitable for carrying out the method according to the invention is shown schematically with the individual devices (A) to (I), the devices (B), (D), (F), (H) and (I), in particular the devices ( H) and (I) are optional.
  • the illustrated diagram of the system suitable for carrying out the method according to the invention comprises the following devices in the sequence listed below: degreasing device (A), optionally rinsing device (B), pickling device (C), optionally rinsing device (D), flux treatment device (E), optionally drying device (F), hot-dip galvanizing device (G), optionally cooling device (H) and optionally post-processing or post-treatment device (I).
  • ad b The plate is completely covered with salts by immersing it in the flux solution. After the drying step, the surface of the component is already slightly dry. As a control, the sheets are weighed after pickling and after drying. In comparison to variant a), it can be seen that the flux film weighs 2.5% less, which is due to a lower residual moisture content as a result of faster drying. After galvanizing, a homogeneous zinc layer is formed without any imperfections.
  • the hot-dip galvanized sheets pretreated with the alcohol-containing flux according to the invention show significantly longer service lives (up to 40% improvement in service life) compared to hot-dip galvanized sheets which use the otherwise identical flux (but without any alcohol content, ie purely aqueous, ie not according to the invention) are pretreated.
  • Example series 1 is repeated, but with a different composition of the galvanizing bath.
  • Example series 1 to 5 are repeated, but with a different flux composition (use of 0.005% by weight or 50 ppm AgCl instead of AlCl 3 ).
  • Example series 1 to 5 are repeated, but with a different flux composition (use of a combination of 0.0025% by weight or 25 ppm AgCI and 0.0025% by weight or 25 ppm AlCl 3 instead of AlCl 3 alone).
  • Example series 1 to 15 are repeated, but with a different flux composition (complete omission of AlCl 3 and AgCI).
  • the zinc layers result in highly inhomogeneous layers with a significant number of defects and clearly visible defect structures.
  • Salinity a total of 200 to 700 g / l, typically 450 to 550 g / l pH in the range of 2.5 to 5
  • For Al 4.2 to 6.2%: typically 2.5 to 3.5
  • For Al 4.2 to 6.2%: typically 50 to 70 ° C
  • For Al up to 1,000 ppm typically 35 to 60 ° C
  • Wetting agent content 0.2 to 5% Solution with a propanol and / or ethanol content of 0.2 to 72%
  • For Al 4.2 to 6.2%: typically 5 to 20%

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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)
EP17710526.9A 2016-06-13 2017-03-13 Verfahren und flussmittel für die feuerverzinkung Active EP3445889B1 (de)

Priority Applications (3)

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PL17710526T PL3445889T3 (pl) 2016-06-13 2017-03-13 Sposób oraz topnik do cynkowania ogniowego
EP20151616.8A EP3663429A1 (de) 2016-06-13 2017-03-13 Anlage für die feuerverzinkung
SI201730480T SI3445889T1 (sl) 2016-06-13 2017-03-13 Postopek in talilo za vroče pocinkanje

Applications Claiming Priority (3)

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DE102016007107 2016-06-13
DE102016111725.0A DE102016111725A1 (de) 2016-06-13 2016-06-27 Verfahren und Flussmittel für die Feuerverzinkung
PCT/EP2017/055798 WO2017215796A1 (de) 2016-06-13 2017-03-13 Verfahren und flussmittel für die feuerverzinkung

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EP20151616.8A Division-Into EP3663429A1 (de) 2016-06-13 2017-03-13 Anlage für die feuerverzinkung
EP20151616.8A Division EP3663429A1 (de) 2016-06-13 2017-03-13 Anlage für die feuerverzinkung

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EP3445889B1 true EP3445889B1 (de) 2020-07-29

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EP (2) EP3663429A1 (es)
JP (1) JP6815494B2 (es)
CN (1) CN109477196B (es)
BR (1) BR112018075934B1 (es)
CA (1) CA3026326C (es)
DE (1) DE102016111725A1 (es)
ES (1) ES2818732T3 (es)
HU (1) HUE052348T2 (es)
MA (1) MA49780A (es)
MX (1) MX2018015470A (es)
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CN107090571B (zh) * 2017-06-18 2018-05-25 荆门宁杰机电技术服务有限公司 一种焊管的外镀锌装置
CN111936659B (zh) 2018-03-28 2022-12-27 杰富意钢铁株式会社 高强度合金化熔融镀锌钢板及其制造方法
DE102020106543A1 (de) 2020-03-11 2021-09-16 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Verzinken eines Bauteils, insbesondere für ein Kraftfahrzeug, sowie Bauteil für ein Kraftfahrzeug
CN112430794A (zh) * 2020-10-31 2021-03-02 张家港扬子江冷轧板有限公司 一种提高镀锡板表面耐蚀性的自软熔装置及方法
CN114182138B (zh) * 2021-12-14 2023-01-03 西安交通大学 一种生物可降解Zn-Mg-Bi锌合金及其制备方法
DE102022100555A1 (de) 2022-01-11 2023-07-13 Seppeler Holding Und Verwaltungs Gmbh & Co. Kg Verfahren zur verbesserten Verzinkung von Bauteilen
CN114717500B (zh) * 2022-03-30 2023-12-01 青岛靓塔钢结构有限公司 一种镀锌单管塔加工工艺
BE1030796B1 (nl) 2022-08-22 2024-03-18 Balak Coatings Nv Werkwijze voor het voorbehandelen van een te verzinken hekwerkpaneel en voorbehandeld hekwerkpaneel
CN116219344B (zh) * 2023-01-15 2024-02-06 宁波市鄞州鑫旺热镀锌有限公司 一种铁基铸件的热镀锌工艺

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CN109477196A (zh) 2019-03-15
BR112018075934B1 (pt) 2023-02-14
JP6815494B2 (ja) 2021-01-20
BR112018075934A2 (pt) 2019-04-09
HUE052348T2 (hu) 2021-04-28
ES2818732T3 (es) 2021-04-13
CN109477196B (zh) 2021-02-19
US11499216B2 (en) 2022-11-15
WO2017215796A1 (de) 2017-12-21
EP3663429A1 (de) 2020-06-10
MA49780A (fr) 2021-04-07
DE102016111725A1 (de) 2017-12-14
MX2018015470A (es) 2019-10-15
JP2019518142A (ja) 2019-06-27
PL3445889T3 (pl) 2021-01-11
CA3026326C (en) 2020-11-10
SI3445889T1 (sl) 2021-01-29
EP3445889A1 (de) 2019-02-27
US20190144983A1 (en) 2019-05-16

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