EP3481976B1 - Procédé de dépôt par placage de revêtements en zinc et en alliage de zinc à partir d'un bain de revêtement alcalin à élimination réduite des additifs de bain organiques - Google Patents

Procédé de dépôt par placage de revêtements en zinc et en alliage de zinc à partir d'un bain de revêtement alcalin à élimination réduite des additifs de bain organiques Download PDF

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Publication number
EP3481976B1
EP3481976B1 EP18702306.4A EP18702306A EP3481976B1 EP 3481976 B1 EP3481976 B1 EP 3481976B1 EP 18702306 A EP18702306 A EP 18702306A EP 3481976 B1 EP3481976 B1 EP 3481976B1
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Prior art keywords
manganese
nickel
zinc
anode
oxide
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EP18702306.4A
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German (de)
English (en)
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EP3481976A1 (fr
Inventor
Volker Wohlfarth
Ralph Krauß
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 SI201830052T priority Critical patent/SI3481976T1/sl
Priority to PL18702306T priority patent/PL3481976T3/pl
Publication of EP3481976A1 publication Critical patent/EP3481976A1/fr
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Priority to HRP20200760TT priority patent/HRP20200760T1/hr
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • 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
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to a process for the galvanic deposition of zinc-nickel coatings from an alkaline coating bath with zinc-nickel electrolytes and organic bath additives, comprising amine-containing complexing agents. Furthermore, the invention relates to the use of materials as anode for the galvanic deposition of a zinc nickel coating from an alkaline coating bath with zinc nickel electrolytes and organic bath additives, comprising amine-containing complexing agents, and a corresponding galvanic device for the deposition of zinc nickel electrolytes.
  • Alkaline zinc and zinc alloy baths are typically not operated with soluble zinc anodes.
  • the zinc is electrochemically oxidized to Zn (II) during anodic operation.
  • the Zn (II) ions formed enter into the soluble zincate complex, Zn [(OH) 4 ] 2- , with the surrounding hydroxide ions.
  • zinc is oxidized to Zn (II) by the alkaline environment with the formation of hydrogen. This means that the zinc anode additionally chemically dissolves due to the above-mentioned redox reaction, which leads to an uncontrolled increase in the Zn (II) concentration in the zinc alloy electrolyte.
  • alkaline zinc and zinc alloy baths are usually operated with insoluble anodes, and zinc is often dissolved in a separate zinc dissolving tank to form Zn (II) and metered into the bath.
  • anode material Materials that are electrically conductive and chemically inert at least to bases are therefore used as the anode material. These include metals such as nickel, iron, stainless steel, cobalt or alloys of the metals mentioned. Another possibility, for example to use the favorable properties of nickel as an anode material, but on the other hand to save costs, is to use galvanically nickel-plated steel anodes (bright nickel-plated steel anodes) with nickel coatings of e.g. 30 ⁇ m layer thickness. The main reaction is the oxidative formation of oxygen at the insoluble anode.
  • organic bath additives such as complexing agents, brightening agents and wetting agents are usually used in addition to the zinc or zinc alloy electrolyte.
  • the anodic oxidation of the organic bath additives can also form undesired by-products such as oxalates, carbonates, etc., which can have a disruptive effect in the galvanic coating process.
  • Amine-containing complexing agents are used in coating baths for the galvanic deposition of a zinc-nickel alloy coating.
  • the nickel is used in the form of Ni (II), which in an alkaline environment forms a poorly soluble nickel hydroxide complex with the surrounding hydroxide ions.
  • Alkaline zinc nickel electrolytes must therefore contain special complexing agents with which Ni (II) forms a complex more preferably than with the hydroxide ions in order to be able to dissolve the nickel in the form of Ni (II).
  • Amine compounds such as triethanolamine, ethylenediamine, diethylenetetramine or homologous compounds of ethylenediamine, such as e.g. Diethylene triamine, tetraethylene pentamine, etc. used.
  • values of up to 1000 mg / l cyanide can be established in the practice electrolyte until a balance of new formation and drag-out is reached.
  • the formation of cyanides is disadvantageous for several reasons.
  • an increased cyanide formation furthermore leads to the problem that undesired complexes can be formed with the bath additives.
  • the cyanide content is very disadvantageous when using a zinc nickel electrolyte, since nickel forms the stable tetracyanonickelate complex, Ni [(CN) 4 ] 2- with the cyanide ions formed, which means that the nickel bound in this complex is no longer used for the deposition Available. Since it is not possible to differentiate between the nickel complexed by the cyanide and the complexed by the amines in the current electrolyte analysis, the increase in the cyanide content in the electrolyte means a reduction in process reliability.
  • the deposition of zinc-nickel alloy coatings with a proportion of 10-16% by weight of nickel provides very good corrosion protection on components made of iron materials and is therefore of great importance for technical corrosion protection.
  • Strongly alkaline electrolytes are used for the deposition of zinc-nickel alloy coatings, in particular for accessories for automobile production, in order to ensure a uniform layer thickness distribution even on complex three-dimensional geometries of the components to be coated.
  • a minimum layer thickness on the component must be maintained, which is usually 5 - 10 ⁇ m.
  • the nickel concentration has to be adjusted in the course of operation according to the cyanide concentration in the electrolyte, since the part of nickel complexed by cyanide is not available for deposition stands. With the increase in the cyanide content in the electrolyte, the nickel content must be adjusted accordingly in order to be able to keep the nickel content in the layer constant.
  • unscheduled additions of nickel salts to the electrolyte must be made. Suitable supplementary solutions are nickel salts, which have a high water solubility. Nickel sulfate solutions are preferably used in combination with various amine compounds.
  • the accumulation of cyanide in a zinc-nickel alloy electrolyte can also have a negative effect on the optical appearance of the deposition.
  • Milky-veiled deposition can occur in the high current density range. This can be corrected in part by higher dosing of brighteners. However, this measure is associated with an increased consumption of brighteners and thus additional costs for the deposition.
  • cyanide concentration in a zinc-nickel alloy electrolyte reaches values of approx. 1000 mg / l, it may also be necessary for the electrolyte to be partially renewed, which in turn increases process costs. In addition, large amounts of old electrolytes are generated in such partial bathroom renewals, which have to be disposed of in a complex manner.
  • the object of the present invention is to provide a process for the galvanic deposition of zinc nickel coatings from an alkaline coating bath with zinc nickel electrolytes and organic bath additives, which method has a reduced anodic oxidation and a concomitant reduced degradation of the organic bath additives which comprise amine-containing complexing agents , as well as a reduced formation of unwanted degradation products, such as cyanides.
  • the method according to the invention should make it possible to be integrated into existing alkaline zinc nickel baths without additional effort and should allow the methods to be operated much more economically.
  • manganese oxide the decisive component for the reduced degradation of the organic bath additives, as well as the reduced formation of cyanides.
  • metallic manganese can also be used, since manganese oxides, often in the form of a brown-black film, are formed in situ during operation as an anode in the alkaline zinc and zinc alloy electrolyte. The manganese oxides formed can exist in different oxidation states.
  • electrodes which are made of metallic manganese or an alloy containing manganese and which are suitable for use as an insoluble anode in an alkaline zinc and zinc alloy bath are suitable.
  • the manganese-containing alloy is preferably selected from a manganese-containing steel alloy or a manganese-containing nickel alloy.
  • the use of a steel alloy containing manganese is particularly preferred.
  • the proportion of alloy in the manganese-containing alloy has a manganese content of at least 5% by weight of manganese, preferably 10-90% by weight of manganese, particularly preferably 50-90% by weight of manganese.
  • Commercially available steel electrodes have e.g. a manganese content of 12% by weight manganese (X120Mn12 with the material number: 1.3401) or 50% by weight manganese (fried iron).
  • electrodes which are made of metallic manganese or an alloy containing manganese
  • electrodes made of an electrically conductive carrier material which is suitable for use as an insoluble anode in an alkaline zinc and zinc alloy bath, with a coating containing metallic manganese and / or manganese oxide are also suitable.
  • the carrier material is preferably selected from steel, titanium, nickel or graphite. In the process according to the invention, the use of steel as a carrier material is particularly preferred.
  • the coating containing metallic manganese and / or manganese oxide has a manganese content of at least 5% by weight of manganese, preferably 10-100% by weight of manganese, particularly preferably 50-100% by weight of manganese, and particularly preferably 80-100% by weight. Manganese, based on the total amount of manganese resulting from metallic manganese and manganese oxide.
  • the metallic manganese and / or manganese oxide-containing coating may therefore, by several methods, including by thermal spraying, cladding, or chemical vapor deposition such as physical vapor deposition (PVD of Engl. Physical vapor deposition) may be applied to the carrier.
  • PVD physical vapor deposition
  • the layer thickness of the coating containing metallic manganese and / or manganese oxide is not decisive here and can vary depending on the process range from a few nanometers (eg using a PVD process) to several millimeters (eg using a thermal spray process).
  • the coating containing metallic manganese and / or manganese oxide can be applied to the carrier by thermal spraying.
  • the Manganese-containing coating material used for thermal spraying can consist both of metallic manganese and of a mixture which contains iron and / or nickel in addition to metallic manganese.
  • the manganese-containing coating material used for thermal spraying preferably has a manganese content of 80% by weight of manganese or more, preferably 90% by weight of manganese or more, particularly preferably 100% by weight of manganese.
  • the manganese-containing coating material is preferably used in a form suitable for thermal spraying, for example as a powder or wire.
  • atomizing gas e.g. compressed air or inert gas such as nitrogen and argon
  • atomizing gas e.g. compressed air or inert gas such as nitrogen and argon
  • the substrate to be coated can be roughened by means of corundum blasting (blasting material is zirconium corundum) before the thermal spraying process.
  • Another possibility is to arrange an additional adhesive base between the carrier and the coating containing metallic manganese and / or manganese oxide.
  • the primer may consist of nickel, for example.
  • the use of an adhesive base further improves the adhesion of the thermally sprayed layer on the carrier.
  • An adhesive primer is preferably applied directly to the surface of the substrate before the manganese-containing coating material is thermally applied is sprayed on.
  • the primer can be produced using the same thermal spraying method as the coating containing metallic manganese and / or manganese oxide, for example flame spraying or arc spraying.
  • the primer is usually created with a layer thickness of 50 - 100 ⁇ m. If an adhesive base is used, the manganese-containing coating material is generally sprayed directly onto the adhesive base.
  • the manganese-containing coating material is generally sprayed directly onto the substrate to be coated.
  • the manganese-containing coating material can be thermally sprayed onto the carrier by means of conventional spraying processes. These include: arc wire spraying, thermo-spray powder spraying, flame spraying, high-speed flame spraying, plasma spraying, autogenous rod spraying, autogenous wire spraying, laser beam spraying, cold gas spraying, detonation spraying and PTWA (plasma transferred wire arc) spraying. These methods are known per se to the person skilled in the art.
  • the manganese-containing coating material can be applied to the carrier in particular by means of flame spraying or arc spraying. Flame spraying is particularly suitable for the use of a powdered manganese-containing coating material.
  • Powder flame spraying distinguishes between self-flowing and self-adhesive powders.
  • the self-flowing powders usually require additional thermal treatment, which significantly increases the adhesion of the spray layer to the carrier.
  • the thermal aftertreatment is usually carried out with acetylene-oxygen burners. Due to the thermal aftertreatment, the spray layer is both gas and liquid tight, which is why the manganese-containing coating material is preferably applied to the carrier by means of powder flame spraying.
  • layer thicknesses of 50 ⁇ m to several millimeters can be applied to the carrier by means of the above-mentioned processes.
  • thermal spraying can be carried out both in an air atmosphere and in an inert gas atmosphere.
  • This can usually be regulated by the type of atomizing gas. If an inert gas, such as nitrogen or argon, is used as the atomizing gas, oxidation of the manganese-containing coating material is largely prevented.
  • a manganese layer made of metallic manganese or a manganese alloy can be applied to the carrier.
  • manganese oxides which represent the active surface, would then form in the course of the galvanic deposition process on the carrier anode with the metallic manganese or manganese alloy layer applied thereon. Alternatively, these can be applied to the carrier in advance.
  • the active surface does not have to form only during the galvanic deposition process, so that a positive effect, ie suppression of the anodic oxidation of the organic bath additives, becomes visible after a short time.
  • a positive effect ie suppression of the anodic oxidation of the organic bath additives
  • the manganese-containing coating material sprayed under an air atmosphere then contains manganese oxides as well as metallic manganese and optionally iron and / or nickel as well as optionally iron oxides and / or nickel oxides or combinations thereof as a layer applied to the carrier.
  • the coating containing metallic manganese and / or manganese oxide can also be applied by cladding, also called welding plating.
  • the manganese-containing coating material used for cladding can consist both of metallic manganese and of a mixture that contains iron and / or nickel in addition to metallic manganese.
  • the manganese-containing coating material preferably has a manganese content of 80% by weight of manganese or more, preferably 90% by weight of manganese or more, particularly preferably 100% by weight of manganese.
  • the manganese-containing coating material is preferably used in a form suitable for cladding, for example as a powder, wire, rod, tape, paste or cored wire.
  • both the coating material and a thin surface layer of the support to be coated are usually melted by suitable energy sources and metallurgically connected to one another.
  • the diffusion and mixing of the coating material with the carrier material creates a non-stick and non-porous layer.
  • Deposition welding essentially differs from thermal spraying in that the surface of the carrier is melted during build-up welding.
  • the manganese-containing coating material can be applied to the carrier by means of conventional build-up welding processes.
  • Suitable energy sources for this include: arc, flame, Joule heat, plasma beam, laser beam and electron beam. These energy sources are known per se to the person skilled in the art.
  • relatively high layer thicknesses of 1 mm and more can be applied to the carrier by means of the above-mentioned processes.
  • the energy source is guided over the carrier in oscillating movements, as a result of which the manganese-containing coating material is then applied in individual layers.
  • cladding can also be carried out under an air atmosphere as well as under an inert gas atmosphere such as nitrogen or argon.
  • a manganese layer made of metallic manganese or a manganese alloy can be applied to the carrier under an inert gas atmosphere.
  • the high temperatures form oxidation products from the manganese-containing coating material used.
  • the layer formed in an air atmosphere then contains, in addition to metallic manganese and optionally iron and / or nickel, also manganese oxides, and optionally iron oxides and / or nickel oxides or combinations thereof.
  • the coating containing metallic manganese and / or manganese oxide can also be applied to the carrier by gas phase deposition, such as physical gas phase deposition (PVD).
  • gas phase deposition such as physical gas phase deposition (PVD).
  • the manganese-containing coating material used for physical vapor deposition is usually metallic manganese, but other manganese-containing solids, such as manganese oxide, which are suitable for this process can also be used.
  • the manganese-containing coating material can be applied to the carrier by means of conventional vapor deposition processes.
  • the processes of physical Deposition from the gas phase include the processes: evaporation, such as thermal evaporation, electron beam evaporation, laser beam evaporation and arc evaporation, sputtering, and ion plating, as well as reactive variants of these processes.
  • the manganese-containing coating material is usually atomized by bombardment with laser beams, magnetically deflected ions, electrons or by arc discharge (e.g. during sputtering) or brought into the gas phase (e.g. during evaporation) in order to subsequently form a solid containing manganese to be deposited on the surface of the substrate to be coated.
  • the process must be carried out under reduced pressure of approximately 10 -4-10 Pa.
  • layer thicknesses of 100 nm - 2 mm can be applied to the carrier using the PVD method.
  • electrodes which consist of a composite material comprising metallic manganese and / or manganese oxide and a conductive material can also be used.
  • a composite material comprising metallic manganese and / or manganese oxide and a conductive material.
  • carbon preferably graphite, can be used as the conductive material.
  • the composite material containing metallic manganese and / or manganese oxide has a manganese content of at least 5% by weight of manganese, preferably at least 10% by weight of manganese, particularly preferably at least 50% by weight of manganese, based on the total amount of manganese resulting from metallic manganese and manganese oxide.
  • the method of manufacturing such a manganese-containing composite electrode is not particularly limited. Common processes such as sintering or pressing with a binder are therefore suitable. Furthermore, the manganese-containing composite electrode can also be produced by incorporating metallic manganese or manganese oxide in foam metal. These methods are known per se to the person skilled in the art.
  • the zinc nickel baths are not particularly limited, provided that they are alkaline and contain organic bath additives which comprise amine-containing complexing agents.
  • the zinc nickel bath is used for the deposition of a zinc nickel coating from an alkaline zinc nickel electrolyte on a substrate connected as a cathode.
  • this typically contains a zinc ion concentration in the range from 5 to 15 g / l, preferably 6 to 10 g / l calculated as zinc, and a nickel ion concentration in the range from 0.5 to 3 g / l, preferably 0.6 to 1, 5 g / l, calculated as nickel.
  • the zinc and nickel compounds used for the production of the zinc nickel electrolyte are not particularly limited.
  • nickel sulfate, nickel chloride, nickel sulfamate or nickel methane sulfonate can be used.
  • the use of nickel sulfate is particularly preferred.
  • the alkaline zinc nickel baths also contain organic bath additives such as complexing agents, brightening agents, wetting agents, etc.
  • Alkaline zinc nickel electrolytes therefore contain special complexing agents for nickel.
  • the complexing agents are not particularly limited, and any known complexing agents comprising amine-containing complexing agents can be used. Amine compounds such as triethanolamine, ethylenediamine, tetrahydroxopropylethylenediamine (Lutron Q 75), diethylenetetramine or homologous compounds of ethylenediamine, such as e.g. Diethylene triamine, tetraethylene pentamine, etc. used.
  • the complexing agent and / or mixtures of these complexing agents is / are usually used in a concentration in the range of 5-100 g / l, preferably 10-70 g / l, more preferably 15-60 g / l.
  • brighteners are usually used in zinc nickel baths. These are not particularly limited, and any known brightener can be used.
  • Aromatic or heteroaromatic compounds such as benzylpyridinium carboxylate or pyridinium-N-propane-3-sulfonic acid (PPS), are preferably used as brighteners.
  • the electrolyte used in the method according to the invention is basic.
  • sodium hydroxide and / or potassium hydroxide can be used to adjust the pH.
  • Sodium hydroxide is particularly preferred.
  • the pH of the aqueous, alkaline solution is usually 10 or more, preferably 12 or more, particularly preferably 13 or more.
  • a zinc nickel bath therefore usually contains 80 - 160 g / l sodium hydroxide. This corresponds to an approximately 2-4 molar solution.
  • the substrate connected as a cathode is not particularly limited, and any known materials suitable for use as a cathode in an electroplating process for depositing a zinc nickel coating from an alkaline electrolyte can be used.
  • substrates made of steel, hardened steel, forged casting or zinc die casting can be used as the cathode.
  • a galvanic device for the deposition of zinc nickel coatings from an alkaline coating bath with zinc nickel electrolytes and organic bath additives which as anode contains an insoluble electrode containing metallic manganese and / or manganese oxide, as described above, and an alkaline coating bath with zinc nickel electrolytes and organic bath additives. comprising amine-containing complexing agents.
  • the device according to the invention does not require that the anode and cathode compartments are separated from one another by membranes and / or separators.
  • the basic bath mix (2 liters of SLOTOLOY ZN 80) had the following composition: Zn: 7.5 g / l as ZnO Ni: 0.6 g / l as NiSO 4 x 6 H 2 O NaOH: 120 g / l
  • SLOTOLOY ZN 81 40 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 82 75 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 87 2.5 ml / l (basic gloss additive)
  • SLOTOLOY ZN 86 1.0 ml / l (top gloss agent)
  • the above-mentioned basic bath batch contains: 10.0 g / l DETA (diethylene triamine), 9.4 g / l TEA (85% by weight triethanolamine), 40.0 g / l Lutron Q 75 (BASF; 75% by weight tetrahydroxopropylethylene diamine) and 370 mg / l PPS (1- (3-sulfopropyl) pyridinium betaine).
  • the bath temperature was set at 35 ° C.
  • the stirring motion during the current efficiency sheet coating was 250 to 300 rpm. In contrast, the stirring movement during the loading sheet coating was 0 rpm.
  • the current densities at the anode and at the cathode were kept constant.
  • SLOTOLOY ZN 85 contains nickel sulfate, as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 contains 63 mg nickel).
  • the NaOH content was determined after 10 Ah / l by acid-base titration and adjusted to 120 g / l in each case.
  • the cyanide was determined using the cuvette test LCK 319 for easily releasable cyanides from Dr. Lange (today Hach company). Easily released cyanides are converted into gaseous HCN by a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.
  • the least amount of cyanide was formed using the Mn oxide anode according to the invention. Even after an enforced amount of electricity of 100 Ah / l, the cyanide content was using the Mn oxide anode according to the invention is only half as high compared to the comparison anodes 1 to 3.
  • Test example 1.2 was carried out under the same conditions as described in test example 1.1.
  • a straight cold-rolled steel sheet (DIN EN 10139/10140; quality: DC03 LC MA RL) with a sheet surface of 1 dm 2, which was connected as the cathode, was coated with a zinc nickel electrolyte using the comparative anodes 1 to 3 and the Mn oxide anode according to the invention.
  • Table 7 shows that with approximately the same nickel alloy content, depending on the cathodic current density applied, after 100 Ah / l loading, a 3 to 8% higher current yield could be achieved by using the Mn oxide anode according to the invention, compared to the comparison anode usually used as a standard anode 2 (bright nickel-plated steel; see table 5).
  • the specified layer thickness on components can thus be achieved in practice in a shorter time. This leads to a significant reduction in process costs.
  • Test example 1.3 was carried out under the same conditions as described in test example 1.1.
  • the deposition of the zinc nickel electrolyte was checked using a Hull cell test according to DIN 50957.
  • the electrolyte temperature was set at 35 ° C.
  • a 250 ml Hull cell was used.
  • Cold-rolled steel DIN EN 10139/10140 (quality: DC03 LC MA RL) was used as the cathode sheet.
  • the cell current was 2 A, the coating time was 15 minutes.
  • Scheme 1 shows the result of the test sheets, which were coated in a bath and were operated with comparison anodes 1 to 3.
  • Scheme 2 shows the result of the test sheet which was coated in a bath which was operated with the Mn oxide anode according to the invention.
  • the Hull cell sheet which was operated with the Mn oxide anode according to the invention (see Scheme 2), shows after 100 Ah / l a semi-glossy to glossy appearance which is uniform over the entire current density range, which is a measure of the still present and undamaged bath additives.
  • the Hull cell sheets made of the zinc-nickel electrolytes of the comparison anodes 1 to 3 only show a semi-glossy to shiny appearance in the range ⁇ 2 A / dm 2 (corresponds to a distance of 4 cm from the right sheet edge to the right sheet edge).
  • the rest of the sheet metal range is from satin to matt.
  • the basic bath mix (2 liters SLOTOLOY ZN 210) had the following composition: Zn: 7.5 g / l as ZnO Ni: 1.0 g / l as NiSO 4 x 6 H 2 O NaOH: 120 g / l
  • SLOTOLOY ZN 211 100 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 212 30 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 215 14 ml / l (nickel solution)
  • SLOTOLOY ZN 213 5 ml / l (basic gloss additive)
  • SLOTOLOY ZN 216 0.2 ml / l (top gloss agent)
  • the above-mentioned basic bath batch contains: 22.4 g / l TEPA (tetraethylene pentamine), 10.2 g / l TEA (85% by weight) and 5.4 g / l Lutron Q 75 (BASF; 75% by weight tetrahydroxopropylethylene diamine) and 75 mg / l PPS (1- (3-sulfopropyl) pyridinium betaine).
  • the bath temperature was set at 28 ° C.
  • the stirring movement during the loading sheet coating was 0 rpm.
  • the current densities at the anode and at the cathode were kept constant.
  • the nickel used in the electrolyte was supplemented with the nickel-containing liquid concentrate SLOTOLOY ZN 215.
  • the SLOTOLOY ZN 215 contains nickel sulfate, as well as the amines triethanolamine, tetraethylene pentamine and Lutron Q 75 (1 ml SLOTOLOY ZN 215 contains 70 mg nickel).
  • the NaOH content was determined after 10 Ah / l by acid-base titration and adjusted to 120 g / l in each case.
  • zinc pellets were introduced into the electrolyte without current. Zinc dissolution occurs due to the alkalinity of the electrolyte.
  • the zinc content was also regularly analyzed analytically using titration in the laboratory.
  • the cyanide was determined using the cuvette test LCK 319 for easily releasable cyanides from Dr. Lange (today Hach company). Easily released cyanides are converted into gaseous HCN by a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.
  • the manganese alloy anode according to the invention was also compared with the comparison anode 2 made of high-gloss nickel-plated steel in the technical center.
  • a newly prepared SLOTOLOY ZN 80 (from Schlötter) electrolyte was operated for about 6 months with four standard anodes made of bright nickel-plated steel (comparison anode 2), a cyanide content in the zinc nickel electrolyte of 372 mg / l being achieved.
  • the standard anodes made of bright nickel-plated steel were replaced by manganese alloy anodes according to the invention exchanged.
  • the zinc nickel electrolyte was then subjected to a further 4 months under the same conditions.
  • the basic bath mix (200 liters SLOTOLOY ZN 80) had the following composition: Zn: 7.5 g / l as ZnO Ni: 0.6 g / l as NiSO 4 x 6 H 2 O NaOH: 110 g / l SLOTOLOY ZN 81: 40 ml / l (complexing agent mixture) SLOTOLOY ZN 82: 75 ml / l (complexing agent mixture) SLOTOLOY ZN 87: 2.5 ml / l (basic gloss additive) SLOTOLOY ZN 83: 2.5 ml / l (basic gloss additive) SLOTOLOY ZN 86: 1.0 ml / l (top gloss agent)
  • the above-mentioned basic bath batch contains: 10.0 g / l DETA (diethylene triamine), 9.4 g / l TEA (85% by weight triethanolamine), 40.0 g / l Lutron Q 75 (BASF; 75% by weight tetrahydroxopropylethylene diamine) and 370 mg / l PPS (1- (3-sulfopropyl) pyridinium betaine).
  • the bath volume was 200 liters.
  • the bath temperature was set at 33 ° C.
  • the current densities at the anode and at the cathode were kept constant.
  • the monthly bath load was 25,000 Ah.
  • the nickel used in the electrolyte was supplemented with the nickel-containing liquid concentrate SLOTOLOY ZN 85.
  • the SLOTOLOY ZN 85 contains nickel sulfate, as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 contains 63 mg nickel).
  • the necessary amount of nickel was determined using suitable analysis methods (e.g. ICP, AAS).
  • zinc pellets were introduced into the electrolyte without current. Zinc dissolution occurs due to the alkalinity of the electrolyte.
  • the zinc content was also regularly analyzed analytically using titration in the laboratory.
  • the sodium hydroxide content in the electrolyte was analyzed analytically regularly (after 5 Ah / l load) by means of titration in the laboratory and supplemented accordingly.
  • the electrolyte is diluted to a certain extent due to carry-over losses and the necessary freezing out of carbonate.
  • the newly prepared SLOTOLOY ZN 80 electrolyte which was operated with four standard anodes made of bright nickel-plated steel (comparison anode 2), had a cyanide content of 372 mg / l after about 6 months.
  • the standard anodes made of bright nickel-plated steel were replaced by manganese alloy anodes according to the invention (defined as "start” in Table 10).
  • the zinc nickel electrolyte was then subjected to a further 4 months under the same conditions.
  • the influence of the manganese alloy anodes according to the invention on the cyanide content and the organic bath additives was examined at intervals of one month each.
  • the cyanide was determined using the cuvette test LCK 319 for easily releasable cyanides from Dr. Lange (today Hach company). Easily released cyanides are converted into gaseous HCN by a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.
  • the degree of gloss of the deposited layer increased as the cyanide content decreased.
  • the metering of fine-grain and gloss additives such as PPS
  • the addition SLOTOLOY ZN 86 which contains PPS, could be reduced from an addition amount of 100 ml during operation with comparison anodes 2 to 60 ml by using the manganese alloy anodes according to the invention.
  • the amines DETA and TEA are used less using the manganese alloy anodes according to the invention than in the comparison anodes 2.
  • the basic bath mix (2 liters of SLOTOLOY ZN 80) had the following composition: Zn: 7.5 g / l as ZnO Ni: 0.6 g / l as NiSO 4 x 6 H 2 O NaOH: 120 g / l
  • SLOTOLOY ZN 81 40 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 82 75 ml / l (complexing agent mixture)
  • SLOTOLOY ZN 87 2.5 ml / l (basic gloss additive)
  • SLOTOLOY ZN 86 1.0 ml / l (top gloss agent)
  • the above-mentioned basic bath batch contains: 10.0 g / l DETA (diethylene triamine), 9.4 g / l TEA (85% by weight triethanolamine), 40.0 g / l Lutron Q 75 (BASF; 75% by weight tetrahydroxopropylethylene diamine) and 370 mg / l PPS (1- (3-sulfopropyl) pyridinium betaine).
  • the bath temperature was set at 35 ° C.
  • the stirring motion during the current efficiency coating was 250 to 300 rpm. In contrast, the stirring movement during the loading sheet coating was 0 rpm.
  • the current densities at the anode and at the cathode were kept constant.
  • the NaOH content was determined after 10 Ah / l by acid-base titration and adjusted to 120 g / l in each case.
  • the cyanide was determined using the cuvette test LCK 319 for easily releasable cyanides from Dr. Lange (today Hach company). Easily released cyanides are converted into gaseous HCN by a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.

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Claims (12)

  1. Procédé pour le dépôt électrolytique de revêtements de zinc-nickel à partir d'un bain de revêtement alcalin avec des électrolytes de zinc-nickel et des additifs de bain organiques, qui utilise en tant qu'anode une électrode insoluble dans le bain, contenant du manganèse métallique et/ou de l'oxyde de manganèse, dans lequel les additifs de bain organiques comprennent des agents complexants contenant une amine, et dans lequel l'électrode
    1) est fabriquée à partir de manganèse métallique ou d'un alliage contenant du manganèse, dans lequel l'alliage contenant du manganèse contient au moins 5 % en poids de manganèse, ou
    2) est fabriquée à partir d'un support électriquement conducteur et d'un manganèse métallique appliqué par-dessus et/ou revêtement contenant de l'oxyde de manganèse, dans lequel le manganèse et/ou le revêtement contenant de l'oxyde de manganèse contient au moins 5 % en poids de manganèse, par rapport à la quantité totale de manganèse obtenue à partir de manganèse métallique et d'oxyde de manganèse, ou
    3) est fabriquée à partir d'un matériau composite qui comprend du manganèse métallique et/ou de l'oxyde de manganèse et un matériau électriquement conducteur, dans lequel le matériau composite contient au moins 5 % en poids de manganèse, par rapport à la quantité totale qui est obtenue à partir de manganèse métallique et d'oxyde de manganèse.
  2. Procédé selon la revendication 1, dans lequel l'alliage contenant du manganèse est choisi parmi un alliage d'acier contenant du manganèse ou un alliage de nickel contenant du manganèse.
  3. Procédé selon l'une quelconque des revendications 1 et 2, dans lequel l'alliage contenant du manganèse contient 10 à 90% en poids de manganèse, le plus préférentiellement de 50 à 90 % en poids de manganèse.
  4. Procédé selon la revendication 1, dans lequel le support électriquement conducteur est choisi parmi l'acier, le titane, le nickel ou le graphite.
  5. Procédé selon l'une quelconque des revendications 1 et 4, dans lequel le manganèse métallique et/ou le revêtement contenant de l'oxyde de manganèse est appliqué sur le support par pulvérisation thermique de manganèse métallique ou d'un mélange de manganèse métallique avec du fer et/ou du nickel.
  6. Procédé selon l'une quelconque des revendications 1 et 4, dans lequel le manganèse métallique et/ou le revêtement contenant de l'oxyde de manganèse est appliqué sur le support par rechargement de manganèse métallique ou d'un mélange de manganèse métallique avec du fer et/ou du nickel.
  7. Procédé selon l'une quelconque des revendications 1 et 4, dans lequel le manganèse métallique et/ou le revêtement contenant de l'oxyde de manganèse est appliqué sur le support par dépôt en phase vapeur.
  8. Procédé selon l'une quelconque des revendications 1 et 4 à 7, dans lequel le manganèse métallique et/ou le revêtement contenant de l'oxyde de manganèse contient 10 à 100 % en poids de manganèse, le plus préférentiellement 50 à 100 % en poids de manganèse, et encore plus préférentiellement de 80 à 100 % en poids de manganèse, par rapport à la quantité totale de manganèse obtenue à partir de manganèse métallique et d'oxyde de manganèse.
  9. Procédé selon la revendication 1, dans lequel le matériau électriquement conducteur du matériau composite est du carbone, de préférence du graphite.
  10. Procédé selon l'une quelconque des revendications 1 et 9, dans lequel le matériau composite contient au moins 10 % en poids de manganèse, de manière particulièrement préférée au moins 50 % en poids de manganèse.
  11. Utilisation de manganèse métallique ou d'un alliage contenant du manganèse tels que définis selon l'une quelconque des revendications 1 à 3, ou d'un support électriquement conducteur avec un revêtement contenant du manganèse métallique appliqué par-dessus et/ou de l'oxyde de manganèse, tels que définis selon l'une quelconque des revendications 1 et 4 à 8, ou d'un matériau composite qui comprend du manganèse métallique et/ou de l'oxyde de manganèse et un matériau électriquement conducteur, tels que définis selon l'une quelconque des revendications 1, 9 et 10, en tant qu'anode pour le dépôt électrolytique de revêtements de zinc-nickel à partir d'un bain de revêtement alcalin avec des électrolytes de zinc-nickel et des additifs de bain organiques comprenant des agents complexants contenant une amine.
  12. Dispositif électrolytique pour le dépôt de revêtements de zinc-nickel à partir d'un bain de revêtement alcalin avec des électrolytes de zinc-nickel et des additifs de bain organiques, qui utilise en tant qu'anode une électrode insoluble, contenant du manganèse métallique et/ou de l'oxyde de manganèse tels que définis selon l'une quelconque des revendications 1 à 10, et un bain de revêtement alcalin avec des électrolytes de zinc-nickel et des additifs de bain organiques, comprenant des agents complexants contenant une amine.
EP18702306.4A 2017-02-07 2018-02-05 Procédé de dépôt par placage de revêtements en zinc et en alliage de zinc à partir d'un bain de revêtement alcalin à élimination réduite des additifs de bain organiques Active EP3481976B1 (fr)

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PCT/EP2018/052779 WO2018146041A1 (fr) 2017-02-07 2018-02-05 Procédé pour le dépôt électrolytique de revêtements de zinc et d'alliage de zinc à partir d'un bain de revêtement alcalin, avec dégradation réduite des additifs organiques du bain

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PL3481976T3 (pl) 2020-11-02
SI3481976T1 (sl) 2020-08-31
TW201842211A (zh) 2018-12-01
US20190376200A1 (en) 2019-12-12
PH12019500424B1 (en) 2019-05-27
ES2790584T3 (es) 2020-10-28
EP3358045A1 (fr) 2018-08-08
JP6644952B2 (ja) 2020-02-12
DK3481976T3 (da) 2020-05-18
PH12019500424A1 (en) 2019-05-27
HRP20200760T1 (hr) 2020-10-16
MX2019002586A (es) 2019-09-18
PT3481976T (pt) 2020-05-18
BR112019004029B1 (pt) 2020-10-27
US11339492B2 (en) 2022-05-24
JP2019530800A (ja) 2019-10-24
RU2724765C1 (ru) 2020-06-25
WO2018146041A1 (fr) 2018-08-16
CN110325669B (zh) 2020-11-03
KR102086616B1 (ko) 2020-03-09
BR112019004029A2 (pt) 2019-08-20
TWI763777B (zh) 2022-05-11
HUE049752T2 (hu) 2020-10-28

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