EP3222757B1 - Procede et dispositif destines a la dissolution de zinc - Google Patents

Procede et dispositif destines a la dissolution de zinc Download PDF

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Publication number
EP3222757B1
EP3222757B1 EP16161938.2A EP16161938A EP3222757B1 EP 3222757 B1 EP3222757 B1 EP 3222757B1 EP 16161938 A EP16161938 A EP 16161938A EP 3222757 B1 EP3222757 B1 EP 3222757B1
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Prior art keywords
zinc
iron
alloy
spraying
layer
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EP16161938.2A
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German (de)
English (en)
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EP3222757A1 (fr
Inventor
Joachim Laatsch
Stefan Henne
Michael Zöllinger
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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Priority to EP16161938.2A priority Critical patent/EP3222757B1/fr
Priority to PL16161938T priority patent/PL3222757T3/pl
Priority to DK16161938.2T priority patent/DK3222757T3/en
Priority to SI201630093T priority patent/SI3222757T1/sl
Publication of EP3222757A1 publication Critical patent/EP3222757A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline compositions for etching other metallic material
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the present invention relates to a method of dissolving zinc or a zinc alloy in an aqueous alkaline solution, a zinc or zinc alloy electroplating method using this method of dissolving zinc or a zinc alloy, and a zinc dissolving apparatus or a zinc alloy.
  • EP 1 972 600 A1 describes a manufacturing method for a carrying device such as a detachment basket, which is used for the dissolution of metals and alloys, in particular zinc.
  • the supporting device has on the surface of an oxide layer, which is formed by immersion in a salt solution, in particular an alkaline solution of an oxidizing agent.
  • One aspect of the invention relates to a method of dissolving zinc or a zinc alloy.
  • metallic zinc, ie zinc (0), or a zinc alloy is brought into electrically conductive contact with an iron layer and immersed with it in whole or in part in an aqueous, alkaline solution.
  • the iron layer consists of an iron material thermally sprayed onto a substrate; it is thus produced in the process by thermal spraying of an iron material onto the substrate.
  • the iron material used for thermal spraying includes metallic iron and / or an iron alloy, and the iron material used for thermal spraying contains at least 60% by weight of iron based on the total weight of the iron material. This iron layer is also referred to below as "thermally sprayed iron layer”.
  • metallic zinc ie zero oxidation state zinc
  • Zn (II) for example as zincate.
  • zinc (0) can also be dissolved out of an alloy so that residues of the alloy remain and not the entire alloy is dissolved. Such a variant is counted according to the invention for "dissolving" a zinc alloy.
  • the zinc or zinc alloy is brought into electrically conductive contact with the thermally sprayed iron layer (cathode). It can be an immediate or indirect spatial contact between zinc or zinc alloy and the iron layer. Direct physical contact occurs when the thermally sprayed iron layer is directly adjacent to the zinc or zinc alloy.
  • An example of this would be a releasing basket coated with the iron layer, for example a steel basket filled with zinc or zinc alloy, for example in the form of pellets, granules or spheres.
  • An indirect spatial contact is present when the thermally sprayed iron layer is not directly adjacent to the zinc or the zinc alloy, that is spaced apart. Such a spacing can be realized for example by means of a spacer, for example a washer. It is also possible to hang the zinc or zinc alloy and the substrate with the thermally sprayed iron layer separately from each other in the bath. The electrically conductive contact between the iron layer and zinc or zinc alloy can then take place via a metallic conductor, for example a metal pin, a metal screw or a cable, which electrically conductively connects the iron layer to the zinc or zinc alloy.
  • a metallic conductor for example a metal pin, a metal screw or a cable, which electrically conductively connects the iron layer to the zinc or zinc alloy.
  • the process enables high zinc dissolution rates which are significantly higher than those of conventional processes in which an untreated steel or iron sheet or a rusted steel sheet is used as the cathode.
  • high levels of zinc dissolution can occur over a long period of time and even at high zinc concentrations in the aqueous alkaline solution be enabled.
  • the erfindungsffleße method allows to provide within a relatively short time a larger amount of dissolved zinc and dissolved zinc in high concentrations. This allows the zinc concentration to be more easily and reliably controlled, for example, in zinc baths used in galvanic processes.
  • the inventors have further found that the above method of dissolving zinc or a zinc alloy is very robust. It shows only a small dependence on the temperature and can be operated at all common for galvanic coating with zinc temperatures. Furthermore, the process is insensitive to the common additives used in zinc baths for electroplating. Organic additives can be readily used. The method is therefore particularly suitable for providing dissolved zinc for galvanic processes.
  • the aqueous, alkaline solution is cyanide-free. It is preferably an alkaline, cyanide-free zinc bath or a zinc electrolyte, which is suitable for the electrodeposition of zinc or zinc alloys.
  • the zinc bath may contain one or more typical additives for alkaline zinc baths, such as brighteners, surfactants, polymers, carbonates, silicates, and chelating agents.
  • the method for dissolving zinc or a zinc alloy can thus be combined with a process for electroplating with zinc or a zinc alloy.
  • scrap metal containing zinc or zinc alloy e.g., scrap metal
  • the scrap contains at least on the surface of metallic zinc or a zinc alloy.
  • zinc or zinc alloy-containing scrap metal are metal having a coating of electrodeposited zinc or electrodeposited zinc alloy, hot-dip galvanized metal and zinc flake-coated metal.
  • the aqueous alkaline solution may contain a hydroxide, for example, an alkali metal hydroxide and / or an alkaline earth metal hydroxide. Preference is given to sodium hydroxide and / or potassium hydroxide.
  • the pH of the aqueous alkaline solution is usually 10 or more, preferably 12 or more, more preferably 13 or more.
  • the zinc to be dissolved or the zinc alloy to be dissolved can basically be present in any desired form, for example in the form of a sheet, a coating on a support, as ingots or in the case of a dissolving basket as pellets, granules, spheres or the like.
  • a zinc alloy preferably contains at least 50% by weight of zinc, more preferably at least 75% by weight of zinc, more preferably at least 95% by weight of zinc, for example 98.0 to 99.9% by weight.
  • the iron layer is a thermally sprayed iron layer. That is, it was obtained by a thermal spray method on the substrate.
  • the production by means of thermal spraying is easy to carry out and associated with less effort than, for example, the production of Raney catalysts, so that there are also economic advantages over the latter.
  • the thermally sprayed iron layer contains iron (0) and at least one or more iron (III) oxygen compounds.
  • Iron (III) oxygen compounds can be detected, for example, in an XPS analysis of a thermally sprayed iron layer.
  • the iron (III) oxygen compounds are formed by thermal spraying of the iron material, that is by reaction of iron with oxygen.
  • the iron (III) oxygen compounds include at least one compound selected from an iron (III) oxide, an iron (III) oxide hydroxide, a ferric hydroxide and combinations thereof. It can be assumed that hydroxide compounds, for example on the surface of the thermally sprayed iron layer, can also be formed in the presence of the aqueous, alkaline solution. After thermal spraying and before use in the aqueous alkaline solution, the sprayed iron layer contains in particular at least one iron (III) oxygen compound selected from iron (III) oxide (Fe 2 O 3 ), iron (III) oxide hydroxide ( FeOOH) or a combination thereof.
  • the iron material used for thermal spraying contains metallic iron and / or an iron alloy.
  • Suitable iron alloys are, in particular, those which contain at least one transition metal other than iron and / or carbon.
  • a suitable iron alloy may also consist of iron and the at least one transition metal and / or carbon.
  • the transition metal is selected, for example, from manganese, nickel, copper, molybdenum, zirconium, and combinations thereof.
  • the iron material used for thermal spraying contains at least 60% by weight of iron.
  • the content of iron refers to both iron in the form of metallic iron, iron alloys described above, and other iron compounds. It thus indicates the total iron content based on the total weight of the iron material used for thermal spraying.
  • the inventors have found that a high iron content in the iron material results in particularly high zinc dissolution rates.
  • the iron material used for thermal spraying therefore contains at least 80% by weight of iron, more preferably at least 90% by weight and even more preferably at least 95% by weight of iron, based on the total weight of the iron material.
  • the iron material used is preferably metallic iron or a steel which, in addition to iron for example, contains small amounts ( ⁇ 5% by weight, in particular ⁇ 2% by weight) of carbon and transition metal. As a result, particularly favorable, environmentally friendly thermally sprayed iron layers can be produced, with which high zinc dissolution rates are made possible.
  • the iron material is preferably used in a form suitable for thermal spraying, for example as a powder or wire.
  • the iron layer has a roughness Ra of at least 4 ⁇ m, preferably 5 to 50 ⁇ m, more preferably 6 to 40 ⁇ m.
  • Ra indicates the arithmetic mean roughness value according to DIN EN ISO 4287: 2010.
  • the roughness of the thermally sprayed iron layer need not result in a very high specific surface area. In some examples, significantly lower specific surface values were found for a thermally sprayed iron layer than for a rusted steel sheet. Since significantly higher zinc dissolution rates were nevertheless observed with a thermally sprayed iron layer, it can be assumed that the specific surface of the thermally sprayed iron layer has only a slight influence on the zinc dissolution rates.
  • the thermally sprayed iron layer has a comparatively positive potential.
  • the thermally sprayed iron layer in 1 M sodium hydroxide solution can have a redox potential of more than +0.6 V if a hydrogen electrode (eg a HydroFlex® hydrogen electrode from Gaskatel) is used as the reference electrode.
  • a hydrogen electrode eg a HydroFlex® hydrogen electrode from Gaskatel
  • the iron layer has an average thickness of 10 ⁇ m to 1000 ⁇ m, preferably 30 ⁇ m to 600 ⁇ m and particularly preferably 50 ⁇ m to 400 ⁇ m.
  • a certain layer thickness is helpful for the strength of the iron layer. If the layer thickness is chosen too large, this in turn may lead to the iron layer flaking off.
  • the average thickness of the iron layer is determined by scanning electron microscopy on a transverse section of the iron layer.
  • the substrate may be a metal, a semiconductor or a nonmetal. Of course, those materials are used which are suitable for the thermal spraying of the iron material, so in particular have a sufficient temperature stability.
  • a substrate made of metal, in particular steel is used. It may for example be in the form of a sheet, preferably in the form of a perforated plate, or in the form of a basket.
  • the substrate is preferably not of a thermally sprayed iron material.
  • the substrate primarily serves to produce a flat iron layer by thermal spraying.
  • the iron layer is supported by the substrate.
  • a primer may be arranged between substrate and the iron layer. This may for example be based on bronze, nickel or a nickel-titanium alloy or consist entirely of it.
  • a primer is preferably applied flatly directly to the substrate before the iron material is thermally sprayed on.
  • the primer may be produced by the same thermal spraying method as the iron layer, for example flame spraying or arc spraying. Usually, the primer is produced with a thickness of up to 50 microns. If a primer is used, the iron material is usually sprayed directly on the primer thermally.
  • the iron material is typically thermally sprayed directly onto the substrate.
  • the iron layer according to one of the embodiments described above can be thermally sprayed onto the substrate (with or without a primer) by means of conventional methods.
  • the iron material according to one of the embodiments described above may be thermally sprayed onto the substrate by one of the following methods: arc wire spraying, thermo spray powder spraying, flame spraying, high velocity flame spraying, plasma spraying, autogenous rod spraying, Autogenous wire spraying, laser spraying, cold gas spraying, detonation spraying and PTWA spraying.
  • arc wire spraying thermo spray powder spraying, flame spraying, high velocity flame spraying, plasma spraying, autogenous rod spraying, Autogenous wire spraying, laser spraying, cold gas spraying, detonation spraying and PTWA spraying.
  • flame spraying is particularly suitable for the use of a pulverulent iron material.
  • arc spraying is suitable.
  • Arc spraying is characterized by a high application rate and low energy consumption. Furthermore, there is a comparatively low substrate heating, so that there is great variability in the substrate used.
  • the thermally sprayed iron layer is therefore preferably produced by means of arc spraying, in particular when working on an industrial scale.
  • the zinc or zinc alloy is brought into electrically conductive contact with the iron layer. This can be done via the Substrate happen when this is electrically conductive and in contact with the zinc or the zinc alloy. Another possibility is to provide a dissolving basket with a thermally sprayed iron layer and to fill the zinc or the zinc alloy in these.
  • the iron layer may also be brought into electrical contact with the zinc or zinc alloy via a metallic conductor.
  • a metallic conductor may be, for example, a metal rod or a metal screw, for example made of steel, copper or another metal, which is not attacked by the aqueous alkaline solution, or the like.
  • the substrate with the iron layer and the zinc. or the zinc alloy in parallel for example, via a spacer such as a washer separated from each other to be arranged.
  • the metallic conductor can then be guided perpendicular thereto by substrate and iron layer and zinc or zinc alloy to produce the electrically conductive contact.
  • the metallic conductor may also pass through the spacer. Another possibility is to make the electrically conductive contact via a cable that connects zinc or zinc alloy with the iron layer or a metallic substrate.
  • the substrate with the thermally sprayed iron layer and the zinc or zinc alloy can be spaced apart from one another.
  • a spacer for example a washer
  • the electrically conductive contact can take place via one or more metallic conductors, for example as described in the preceding paragraph.
  • the spacing can thus be designed so that the contact surface with the aqueous, alkaline solution of the substrate with the Iron layer and the zinc or zinc alloy is relatively large.
  • the process for dissolving zinc or a zinc alloy is very robust. It can be carried out successfully over a wide temperature range.
  • the aqueous alkaline solution may, for example, have a temperature of 10 to 90 ° C, preferably 15 to 75 ° C, particularly preferably 20 to 60 ° C.
  • the process can be readily operated at temperatures typical of galvanic zinc baths, especially in the range of 10 to 60 ° C, preferably 15 to 50 ° C and more preferably 20 to 40 ° C. At such temperatures, the additives commonly used in zinc baths are stable. If this need not be taken into account, for example, if the dezincification of scrap metal only a simple caustic solution is used, then higher temperatures can be used.
  • the aqueous, alkaline solution is mixed during the process. This can be done, for example, by stirring, circulation or (partial) replacement of the aqueous, alkaline solution.
  • the immersion depth can be varied into the aqueous, alkaline solution.
  • zinc or zinc alloy and substrate having the thermally sprayed iron layer can be easily taken out of the aqueous alkaline solution, or the aqueous alkaline solution is drained.
  • the method for dissolving zinc or a zinc alloy can be easily carried out on an industrial scale.
  • the process coats a component or other electrically conductive body with zinc or a zinc alloy.
  • the deposited zinc alloy may differ from the zinc alloy used for dissolution.
  • the method of electrodeposition benefits from the above-described advantages of the method of dissolving zinc or a zinc alloy.
  • step (A) and (B) are preferably performed spatially separated from each other.
  • step (B) may be performed in a separate compartment.
  • the zinc-containing aqueous alkaline solution may then be supplied as needed to the zinc bath used for coating to supply dissolved zinc, which is consumed in electroplating.
  • steps (A) and (B) can thus be carried out at the same time or else offset in time.
  • the galvanic coating with zinc or a zinc alloy from a zinc-containing, aqueous, alkaline solution, in particular a cyanide-free zinc bath, is known per se to a person skilled in the art.
  • the container for example a tub, is thus large enough in terms of dimensions that the arrangement fits in whole or in part.
  • This arrangement or the device is suitable for dissolving zinc or a zinc alloy.
  • an aqueous, alkaline solution preferably an alkaline, cyanide-free zinc bath, is then filled into the container and the assembly wholly or partially immersed therein.
  • the container preferably contains an opening for filling and a closable outlet in order to drain the aqueous alkaline solution.
  • the device preferably comprises means with which the depth of immersion of the arrangement into the aqueous, alkaline solution can be controlled during operation of the device.
  • the arrangement can then be removed completely from the aqueous alkaline solution to interrupt the dissolution process.
  • the control can be effected, for example, by the arrangement being suspended at different heights.
  • the aqueous alkaline solution can also be partially or completely drained.
  • the device comprises means for mixing the aqueous alkaline solution during the dissolution process.
  • the device can, for example, comprise means for stirring, circulating or for a (partial) replacement of the aqueous, alkaline solution.
  • the device may also include means to regulate the temperature in the aqueous alkaline solution.
  • the device can be combined with a galvanic bath.
  • the in Fig. 1 recorded XPS spectra of a thermally sprayed iron layer.
  • a thermally sprayed iron layer was analogously to Example 4, a steel sheet without primer coated by arc spraying.
  • an iron arc wire was used as the iron material.
  • the average layer thickness was about 200 ⁇ m.
  • iron (III) compounds were mainly detected in all measurements.
  • the iron (III) oxygen compounds FeOOH and Fe 2 O 3 could be detected. It is noticeable that more iron (III) oxygen compounds were found on the surface of the thermally sprayed iron layer than in the interior of the layer.
  • the XPS analysis was performed on an XPS Quantum 2000 system equipped with a 180 ° hemispheric analyzer and a 16 channel detector.
  • the spectra were recorded by a focused, monochromatic X-ray source (Al-K ⁇ , 1486.68 eV) with a beam diameter of 50 ⁇ m and a power of 12 W.
  • the pressure in the analysis chamber was about 5 ⁇ 10 -7 Pa.
  • the instrument was operated in FAT mode of the analyzer with a 45 ° electron take-off angle to the surface normal.
  • the samples were neutralized using an electron gun (cold cathode 1.2 eV) and a low energy Ar ion beam (10 eV).
  • a sputter cleaning was performed using an Ar ion beam with an energy of 2 kV, rastered over the area of 3 x 3 mm.
  • Fig. 2A and Fig. 2B show SEM images of the surface of the above-described thermally sprayed iron layer Fig. 1 at a 500 times ( Fig. 2A ) and at a 100x magnification ( Fig. 2B ). These images clearly show a rough surface structure formed by the particles spun during thermal spraying.
  • FIGS. 4A and 4B show SEM images at 100x magnification ( Fig. 4A ) and at 500X magnification of a cross section of a thermal sprayed iron layer according to another embodiment of the invention.
  • a steel sheet (5) was first provided with a primer made of nickel-titanium alloy.
  • the primer was applied by arc spraying.
  • an iron arc wire was applied as iron material by arc spraying as a thermal spraying method.
  • the average layer thickness of the thermally sprayed iron layer was about 250 to 300 microns.
  • the preparation was carried out analogously to Example 5.
  • FIG. 4B For example, a part of the primer with "6”, grain edges of spin iron particles with "7” and “8” and a spot inside such a grain are marked with "9". In each case an EDX measurement was carried out at these locations. The corresponding spectra are in the Figs. 5A to 5D in this order. In the lower part of Fig. 4B the steel substrate (5) can be seen.
  • Iron (0) and iron (III) oxygen compounds were detected at the grain boundaries of spin-coated iron particles, marked “7” and “8” respectively, which is reflected in the Fig. 5B and 5C you can see.
  • Fig. 5D In the interior of a grain, at the location "9”, mainly iron was found ( Fig. 5D ).
  • the iron particles spun on thermal spraying were oxidized, especially at the surface.
  • the roughness of an uncoated strip steel sheet, a rusted steel sheet and two thermally sprayed iron layers according to the invention were measured analogously to DIN EN ISO 4287: 2010.
  • a confocal microscope psurf explorer from NanoFocus AG was measured and then evaluated in accordance with DIN EN ISO 4287: 2010.
  • the thermally sprayed iron layers according to the invention were produced with an iron powder (Example 2) or an iron wire (Example 4) as iron material.
  • Table 1 sample Average Average Average Ra [ ⁇ m] Rt [ ⁇ m] Rz [ ⁇ m] Uncoated steel sheet (Comparative Example 1) 0.2 2.1 1.5 Rusted steel sheet (Comparative Example 8) 0.9 19.8 11.3 Iron layer (iron powder, example 2) 7.1 71, 0 43.5 Iron layer (iron wire, example 4) 22.6 180.0 121.0
  • the specific surface area denotes a BET specific surface measured in accordance with DIN ISO 9277 (krypton at 77 K).
  • Table 2 sample specific surface [m 2 / g] Uncoated steel sheet (Comparative Example 1) not definable Rusted steel sheet (Comparative Example 8) 0.2171 ⁇ 0.0021 Iron layer (iron wire, example 4) 0.0141 ⁇ 0.0001
  • the steel sheet was then thermally sprayed by arc spraying.
  • an iron wire so-called iron arc wire with 0.7 wt.% Mn, 0.07 wt.% C and the balance Fe, diameter 1.6 mm
  • arc temperature 3000 to 4000 ° C at the burner head
  • compressed air (6 bar
  • a steel sheet (A 0.175 dm 2 ) was degreased.
  • Example 1 Compared to a bare steel sheet as a cathode (Comparative Example 1, curve (2)), the cathode according to the invention with a thermally sprayed iron layer (Example 1, curve (1)) gave a significantly higher current flow. This means that a correspondingly higher zinc dissolution rate than in Comparative Example 1 was achieved. After 1 hour, the current flow in Example 1 was higher by a factor of 13.5 than in Comparative Example 1 (see Fig. 6 ). During the flow of electricity in Comparative Example 1 presumably then dropped sharply due to the higher zinc concentration, it remains relatively constant in Example 1 at a high level.
  • Example 1 After 15 hours, at the end of the measurement, the current flow is a flow of current of 1.048 A / dm 2 over 0,025 A / dm 2 was in Example 1 with the inventive iron layer by a factor of 40 higher than in Comparative Example 1. It was measured.
  • the steel perforated plate was preheated with a welding torch to approx. 300 ° C and then thermally sprayed by means of flame spraying.
  • an iron powder (-325 mesh, 97% from Sigma-Aldrich) was fed to the flame, which was operated with an acetylene-oxygen mixture (burner flame temperature was about 2000 ° C), and by compressed air (maximum 3 bar ) from a distance of 15 to 20 cm sprayed onto the steel perforated plate.
  • With a pivoting movement (about 50 to 100 mm / s) was coated until a uniform, about 300 microns thick thermally sprayed iron layer has been produced.
  • an aqueous, alkaline, cyanide-free zinc bath (5 L) (20) was used in each case as the electrolyte at 25 ° C. by means of a magnetic stir bar (22) and an in Fig. 7 Magnetic stirrer, not shown, mixed at 1000 rpm.
  • the zinc bath contained in each case 8 g / L Zn (II), 120 g / L NaOH, 40 g / L Na 2 CO 3 and 20 mL / L ZINCASLOT 81 (a basic additive for the novel preparation of an electrolyte from Dr.-Ing Schlotter GmbH & Co. KG).
  • the zinc bath thus corresponds to a typical zinc bath used in electroplating.
  • a zinc anode (19.8 ⁇ 5 ⁇ 1 cm with A 2.48 cm 2 ) (15) with a steel screw (17) and associated nut (18) made of steel at the respective cathode was used to produce the electrically conductive contact (16) fixed in parallel and immersed in a hook (23) made of polypropylene (PP) entirely in the electrolyte.
  • PP polypropylene
  • Examples 2 to 10 show that dissolution of zinc by the process of the present invention gives significantly higher zinc dissolution rates than using a conventional steel sheet or a rusted steel sheet. As compared with rusted steel (Comparative Example 8), an increase of up to 350% was observed. With respect to uncoated steel (Comparative Example 7), even increases by a factor of 20 could be observed.
  • test specimen 1 In a Petri dish (1000 mL) with aqueous NaOH solution (500 mL), the respective cathode of Example 3 and Comparative Example 8 was placed. Then, in direct contact over the base of the cathode, a test piece to be dezincified was centered.
  • the test specimens each had the dimensions 30 mm ⁇ 40 mm ⁇ 6 mm and were galvanized with a galvanically deposited zinc layer approximately 30 ⁇ m thick (test specimen 1) or hot-dip galvanized with a zinc layer approximately 100 ⁇ m thick (test specimen 2).
  • T the temperature
  • concentration of the sodium hydroxide solution ([NaOH]) were varied and the removal of the zinc coating per unit time (contact time t) was balanced.
  • the dezincing carried out by the process according to the invention which uses an iron layer produced by thermal spraying on a substrate as the cathode, shows significantly higher zinc removals under comparable conditions. That is, more zinc per unit time can be removed from the test body.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Claims (14)

  1. Procédé servant à dissoudre du zinc ou un alliage de zinc (15), où
    - une couche de fer (16) est produite sur un substrat par injection thermique d'un matériau en fer,
    dans lequel le matériau en fer utilisé pour l'injection thermique comprend du fer métallique et/ou un alliage de fer et
    dans lequel le matériau en fer utilisé pour l'injection thermique contient au moins 60 % en poids de fer par rapport au poids total du matériau en fer ;
    - du zinc métallique ou un alliage de zinc (15) est amené en contact électrique avec la couche de fer (16) et est plongé avec celle-ci en totalité ou en partie dans une solution (20) aqueuse alcaline.
  2. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon la revendication 1, dans lequel la solution aqueuse alcaline est un bain de zinc (20) alcalin sans cyanure.
  3. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon la revendication 1 ou 2, dans lequel la couche de fer (16) comprend du fer (0) et un ou plusieurs composés de fer (III)-oxygène.
  4. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon la revendication 3, dans lequel le composé de fer (III)-oxygène comprend au moins un composé, choisi parmi un oxyde de fer (III), un hydroxyde d'oxyde de fer (III), un hydroxyde de fer (III) et des combinaisons de ceux-ci.
  5. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 4, dans lequel l'alliage de fer comprend un métal de transition autre que le fer, de manière préférée choisi parmi le manganèse, le nickel, le cuivre, le molybdène, le zirconium et des combinaisons de ceux-ci, et/ou du carbone.
  6. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 5, dans lequel le matériau en fer utilisé pour l'injection thermique contient au moins 80% en poids de fer, de manière préférée au moins 90 % en poids de fer, de manière davantage préférée au moins 95 % en poids de fer, par rapport au poids total du matériau en fer.
  7. Procédé servant à dissoudre du zinc ou un alliage de zinc selon l'une quelconque des revendications 1 à 6, dans lequel la couche de fer (16) présente une rugosité Ra d'au moins 4 µm, dans lequel Ra est la rugosité moyenne arithmétique selon la norme DIN EN ISO 4287:2010.
  8. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 7, dans lequel la couche de fer (16) présente une épaisseur moyenne allant de 10 µm à 1 000 µm, définie par microscopie électronique à balayage (MEB) au niveau d'une coupe transversale de la couche de fer.
  9. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 8, dans lequel le substrat est composé de métal, de manière préférée d'acier.
  10. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 9, dans lequel une base adhésive à base de bronze, de nickel ou d'un alliage de nickel-titane est disposée entre le substrat et la couche de fer (16).
  11. Procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 10, dans lequel pour produire la couche de fer (16), le matériau en fer est appliqué par injection thermique sur le substrat au moyen d'un des procédés suivants : projection à l'arc électrique, pulvérisation thermique de poudre, projection à la flamme, projection à la flamme à haute vitesse, procédé de pulvérisation par plasma, projection à la baguette autogène, projection au fil autogène, projection par laser, projection de gaz à froid, projection par détonation et projection par arc de soudure transféré plasma.
  12. Procédé servant à revêtir de manière galvanique avec du zinc ou un alliage de zinc, comprenant :
    (A) la séparation galvanique du zinc ou d'un alliage de zinc d'une solution aqueuse alcaline, qui contient du zinc dissous et éventuellement d'autres métaux dissous, sur un composant ou un autre corps électroconducteur pour revêtir le composant ou le corps électroconducteur de zinc ou d'un alliage de zinc, et
    (B) la mise en oeuvre d'un procédé servant à dissoudre du zinc ou un alliage de zinc (15) selon l'une quelconque des revendications 1 à 11 pour fournir du zinc dissous pour l'étape (A).
  13. Dispositif servant à dissoudre du zinc ou un alliage de zinc (15), comprenant un ensemble avec une anode de zinc (15), une couche de fer en tant que cathode (16), qui est en contact électroconducteur avec l'anode de zinc (15), dans lequel
    - l'anode de zinc (15) comprend du zinc métallique ou un alliage de zinc, et
    - le dispositif comprend un contenant (21), qui est adapté pour recevoir une solution (20) aqueuse alcaline, dans laquelle l'ensemble peut être plongé en totalité ou en partie,
    caractérisé en ce que
    la couche de fer (16) est constituée d'un matériau en fer appliqué par injection thermique sur un substrat,
    dans lequel le matériau en fer utilisé pour l'injection thermique comprend du fer métallique et/ou un alliage de fer et
    dans lequel le matériau en fer utilisé pour l'injection thermique contient au moins 60 % en fer par rapport au poids total du matériau en fer.
  14. Dispositif servant à dissoudre du zinc ou un alliage de zinc (15) selon la revendication 13, dans lequel
    - la couche de fer (16) est une couche de fer (16) comme définie dans l'une quelconque des revendications 4 à 9, et/ou
    - le substrat est composé de métal, de manière préférée d'acier,
    et/ou
    - une base adhésive à base de bronze, de nickel ou d'un alliage de nickel-titane est disposée entre le substrat et la couche de fer (16).
EP16161938.2A 2016-03-23 2016-03-23 Procede et dispositif destines a la dissolution de zinc Active EP3222757B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16161938.2A EP3222757B1 (fr) 2016-03-23 2016-03-23 Procede et dispositif destines a la dissolution de zinc
PL16161938T PL3222757T3 (pl) 2016-03-23 2016-03-23 Sposób i urządzenie do rozpuszczania cynku
DK16161938.2T DK3222757T3 (en) 2016-03-23 2016-03-23 METHOD AND DEVICE FOR SOLUTION OF ZINC
SI201630093T SI3222757T1 (sl) 2016-03-23 2016-03-23 Postopek in naprava za raztapljanje cinka

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16161938.2A EP3222757B1 (fr) 2016-03-23 2016-03-23 Procede et dispositif destines a la dissolution de zinc

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EP3222757B1 true EP3222757B1 (fr) 2018-09-19

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EP3904563A1 (fr) 2020-04-28 2021-11-03 Dr.Ing. Max Schlötter GmbH & Co. KG Dispositif de dissolution, panier de dissolution, installation de galvanisation et procédé de dissolution de zinc

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
CA2027656C (fr) 1990-10-15 1998-09-29 Rodney L. Leroy Dezingage galvanique d'acier galvanise
DE29605315U1 (de) 1996-03-21 1996-05-30 Surtec Gmbh Vorrichtung zum Auflösen von unedlen Metallen
DE10010316C2 (de) * 2000-02-25 2003-12-04 Siemens Ag Verfahren zum außenstromlosen Auflösen von Zink
CN1172011C (zh) * 2001-09-17 2004-10-20 中国人民解放军海军工程大学 耐海水腐蚀用于热喷涂的锌合金及工艺
DE102004038650B4 (de) 2004-08-09 2006-10-26 Coutelle, Rainer, Dr. Verfahren zur Auflösung von Zink in Laugen
US20070278108A1 (en) * 2006-06-01 2007-12-06 General Electric Company Method of forming a porous nickel coating, and related articles and compositions
EP1972600A1 (fr) * 2007-03-21 2008-09-24 MDC Max Dätwyler AG Bleienbach Système de transport pour la galvanoplastie

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DK3222757T3 (en) 2018-10-29
EP3222757A1 (fr) 2017-09-27
SI3222757T1 (sl) 2018-12-31

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