EP2975162B1 - Method for providing a workpiece with a protective coating - Google Patents

Method for providing a workpiece with a protective coating Download PDF

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Publication number
EP2975162B1
EP2975162B1 EP14177678.1A EP14177678A EP2975162B1 EP 2975162 B1 EP2975162 B1 EP 2975162B1 EP 14177678 A EP14177678 A EP 14177678A EP 2975162 B1 EP2975162 B1 EP 2975162B1
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EP
European Patent Office
Prior art keywords
nickel
bath
layer
nickel layer
workpiece
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP14177678.1A
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German (de)
French (fr)
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EP2975162A1 (en
Inventor
Wolf-Dieter Franz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Franz Oberflaechentechnik GmbH and Co KG
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Franz Oberflaechentechnik GmbH and Co KG
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Priority to EP14177678.1A priority Critical patent/EP2975162B1/en
Publication of EP2975162A1 publication Critical patent/EP2975162A1/en
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Classifications

    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D21/06—Filtering particles other than ions
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Definitions

  • the invention relates to the protective coating of a workpiece with nickel.
  • the workpiece may, for example, be a metallic workpiece which is to be protected against corrosion by the protective coating.
  • a nickel coating system for anticorrosive coating is known in which on an inner nickel layer having a reduced sulfur content, a sulfur-containing nickel layer and on this another nickel layer is arranged. On this three-layer system then a conventional chrome coating is applied.
  • the DE 19 900 715 A1 deals with the cleaning and filtration of electrolyte solutions, in particular with regard to the disposal of residues.
  • the present invention has for its object to provide an advantageous method for protective coating of a workpiece.
  • this object is achieved by a method according to claim 1.
  • the decisive factor is therefore that the first bath is free of sulfur-containing additives, resulting in a sulfur-free first nickel layer.
  • the workpiece is preferably a metallic workpiece, for example of a light metal or a light metal alloy, for example based on aluminum, for example aluminum, or of an iron or steel material, for example of non-stainless steel ,
  • the workpiece per se for example, be provided from a non-conductive plastic material, which is provided with a metal coating, which is then coated according to the invention.
  • Both the first and second nickel layers are deposited in a nickel sulfate-based bath, so at least some of the nickel ions in the bath of nickel sulfate (NiSO 4 ) are provided.
  • the first bath is free of sulphurous additives, with no consideration of sulphate.
  • the first bath has sulphate and nickel ions, but apart from the sulphate no further sulphurous constituent (so it is free).
  • the second bath to a sulfur-containing additive, wherein the sulfate is again disregarded.
  • the second one Bath so nickel and sulfate ions and in addition to a sulfur-containing additive, which is different from the sulfate.
  • the inventor has found that the corresponding (sulfur-free) deposited first nickel layer grows rather irregular, for example, with a columnar structure. It may be, for example, that due to a irregular growth of the first nickel layer results in a protective coating, which then has a non-planar surface as a whole.
  • the first nickel layer may be non-planarizing in nature. Although this may be disadvantageous, for example, in decorative terms, but a corresponding protective layer system just shows a very good corrosion resistant wedge.
  • the first and the second bath are both provided on a water basis, so it is in each case an aqueous solution of the ions mentioned in more detail below. So far as this is the case of the fact that a bath consists exclusively of certain ingredients, this refers to these ingredients in aqueous solution and the water is not always listed as a component again.
  • the first bath in order to obtain a correspondingly high-purity first nickel layer, is filtered during the electrodeposition (during the application of the first nickel layer), preferably by means of an activated carbon filter.
  • an activated carbon filter For example, organic contaminants can be removed.
  • the first bath is ideally pumped continuously through the filter, preferably through a filter with activated charcoal (plates).
  • the flow through the filter is preferably chosen such that the first bath is recirculated at least 3 times in one hour, more preferably at least 5 times, 7 times and 9 times in this order. Possible upper limits may be, for example, at a maximum of 30, 25, 20, 15, 13 or 11 revolutions per hour.
  • the "circulating" means that the x-fold volume (corresponding to the x-times circulation) of the first bath is pumped through the filter in one hour, so just a corresponding flow is set.
  • a plurality of batches are successively coated in the first bath, and the first bath is continuously filtered during that time, preferably also between batches.
  • Each batch can then of course Also, several workpieces may be provided, so several workpieces can be coated in parallel.
  • a cleaning of the first bath before the electrodeposition is provided according to the invention, wherein a metal part (as a cleaning part) is introduced into the first bath and energized.
  • a metal part as a cleaning part
  • metallic impurities can be removed from the first bath, which may have been introduced, for example, during the coating of the preceding batch.
  • the current density on the cleaning metal part is preferably at least 0.05 A / dm 2 , more preferably at least 0.08 A / dm 2 , and possible upper limits are for example at most 0.2 A / dm 2 , preferably at most 0.15 A. / dm 2 , more preferably at most 0.12 A / dm 2 (an upper limit may also be independent of a lower limit of interest, and vice versa).
  • This cleaning with the cleaning metal part does not have to be done before each batch, but preferably a plurality of batches may be successively coated without cleaning therebetween, and a cleaning may be performed before these plurality of batches and another then afterwards before a further plurality of batches.
  • the workpiece Before being introduced into the first bath, the workpiece is chemically pre-nickel-plated in a preferred embodiment, particularly preferably a workpiece based on aluminum.
  • the first nickel layer preferably has a thickness of at least 5 ⁇ m, in this order increasingly preferably at least 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m or 13 ⁇ m, of which independent, preferred upper limits For example, in this order are increasingly preferred at most 20 microns, 19 microns, 18 microns and 17 microns.
  • the provision of a lower limit can generally also be disclosed independently of the provision of an upper limit, and vice versa.
  • the second nickel layer preferably has a thickness of at least 5 ⁇ m, in this order increasingly preferably at least 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m or 13 ⁇ m; preferred upper limits are for example in this order increasingly preferably at most 20 microns, 19 microns, 18 microns and 17 microns. Also in this case, the provision of an upper limit may generally be preferred independently of the provision of a lower limit, and vice versa.
  • the current density in the electrodeposition on the workpiece is at least 0.1 A / dm 2 , preferably at least 0.3 A / dm 2 , especially at least 0.4 A / dm 2 .
  • Advantageous upper limits for example, in this order increasingly preferably at most 2 A / dm 2 , 1.8 A / dm 2 , 1.6 A / dm 2 , 1.4 A / dm 2 , 1.2 A / dm 2 , 1 A / dm 2 , 0.8 A / dm 2 and 0.6 A / dm 2 are.
  • the provision of an upper limit should again generally be disclosed independently of the provision of a lower limit, and vice versa.
  • the sulfur-containing additive in the second bath is a brightener additive, that is to say a so-called brightener, with saccharin being particularly preferred as brightener additive.
  • the first bath is correspondingly free of saccharin or sulfur-containing brightener additives or preferably of brightener additives in general.
  • the brightener preferably the saccharin, in a preferred embodiment with a concentration of at least 2.5 g / l, preferably at least 3.5 g / l, more preferably at least 4 g / l before.
  • Advantageous upper limits may be, for example, at most 15 g / l, in this order increasingly preferably at most 13 g / l, 11 g / l, 9 g / l, 7 g / l and 6 g / l, respectively (the provision of an upper limit again generally be disclosed independently of the provision of a lower limit, and vice versa).
  • the nickel concentration is preferably at least 40 g / l, more preferably at least 50 g / l or 60 g / l, particularly preferably at least 65 g / l.
  • Advantageous upper limits may be, for example, in this order increasingly preferably at most 150 g / l, 130 g / l, 110 g / l, 90 g / l, 80 g / l and 75 g / l (the provision of an upper limit in general again be disclosed independently of the provision of a lower limit, and vice versa).
  • the nickel ions in the second bath are provided not only by the nickel sulfate but also by nickel chloride (NiCl 2 ), wherein the chloride concentration (the chloride ion) is preferably at least 10 g / L, more preferably at least 15 g / l, more preferably at least 20 g / l should be.
  • Advantageous upper limits may be, for example, at most 50 g / l, preferably at most 40 g / l, more preferably at most 30 g / l (the provision of an upper limit should in turn also be disclosed independently of the provision of a lower limit, and vice versa).
  • the nickel in the second bath is provided solely by nickel sulfate and nickel chloride.
  • boric acid is also provided in the second bath, preferably at a concentration of at least 40 g / l, more preferably at least 50 g / l, particularly preferably at least 55 g / l.
  • Advantageous upper limits may be, for example, in this order increasingly preferably at most 100 g / l, 90 g / l, 80 g / l, 70 g / l and 65 g / l (the provision of an upper limit may in turn also be independent of the provision a lower limit, and vice versa).
  • the second bath therefore preferably has nickel, chloride and sulfate ions, boric acid and a brightener, preferably saccharin.
  • the second bath consists exclusively of these components, optionally one apart from a better wetting of the surface to be coated wetting agents (and the water).
  • the nickel concentration is preferably at least 40 g / l, more preferably at least 45 g / l, particularly preferably at least 50 g / l.
  • Advantageous upper limits may be, for example, in this order increasingly preferably at most 80 g / l, 70 g / l and 60 g / l (the provision of an upper limit may generally be preferred regardless of providing a lower limit, and vice versa).
  • the chloride concentration in the first bath may be, for example, at least 10 g / l, preferably at least 20 g / l, more preferably at least 25 g / l, with advantageous upper limits (in the order of their naming increasingly preferred) at about 50 g / l , 40 g / l and 30 g / l respectively (and in general the provision of an upper limit may also be of interest irrespective of the provision of a lower limit, and vice versa).
  • the concentration of boric acid is preferably at least 20 g / l, more preferably at least 30 g / l, more preferably at least 35 g / l, with favorable upper limits (in the order of their nomination increasingly preferred) about at most 70 g / l, 60 g / l, 50 g / l and 45 g / l respectively (and the provision of an upper limit may again be of interest irrespective of the provision of a lower limit, and vice versa).
  • the second bath is preferably composed exclusively of nickel, sulfate and chloride ions and boric acid.
  • the black chromium layer provided in a preferred embodiment as a cover layer preferably has a thickness of at least 0.5 ⁇ m and of at most 1.5 ⁇ m (the upper limit may in turn be independent of the lower limit of interest, and vice versa).
  • layer thicknesses are generally referred to in the present disclosure, these relate in each case to the finished layer, ie the layer thickness at the end / after the deposition (ie not at an intermediate thickness during the deposition).
  • the thickness is taken perpendicular to the surface of the workpiece, and in the case of a layer having varying thickness over the surface of the workpiece, an average value is considered.
  • the invention also relates to a correspondingly protective-coated workpiece, that is to say a workpiece having a first nickel layer, a second nickel layer on the first nickel layer (which adjoins the first nickel layer) and a cover layer on the second nickel layer (US Pat. which adjoins the second nickel layer).
  • the first nickel layer is free of sulfur
  • the second nickel layer has a mass fraction of at least 0.05 wt .-%, preferably at least 0.07 wt .-%, particularly preferably at least 0.08 wt .-%, Has. Possible upper limits are for example at most 0.15 wt .-%, preferably at most 0.12 wt .-%, particularly preferably at most 0.1 wt .-%.
  • sulfur content should also be expressly disclosed with regard to the process category, that is, a first nickel layer which is free of sulfur and a second nickel layer is deposited, which has a corresponding minimum sulfur content (and preferably also a maximum content disclosed herein).
  • the invention also expressly relates to a workpiece that has been protective coated in a method disclosed herein.
  • the inventor has a comparatively observed large electrochemical potential difference between the two nickel layers. This is at least 160 mV, preferably at least 170 mV, with possible upper limits, for example, at most 260 mV, 240 mV, 220 mV, 200 mV or 190 mV can be.
  • the first nickel layer consists exclusively of nickel.
  • This large potential difference corresponds with the observed good corrosion resistance.
  • the latter is not impaired by the black chromium layer, which is preferably provided as a cover layer, and may even be improved to some extent.
  • a particular advantage of this protective coating is that it protects against corrosion on the one hand and is electrically conductive on the other hand.
  • the workpiece in a preferred embodiment is an electrical connection part that can be screwed and / or plugged in, that is, for example, a connector for a power and / or data line.
  • the protective coating is relatively ductile, which can help prevent cracking and spalling. According to current knowledge, this is at least attributable to the highly pure deposited first nickel layer. In a connector that is also bolted, the thread can represent the most mechanically stressed area. In a test on such a connector, the protective coating was also there after 500-times SSverbinden and loosening still intact, which is also due to the high ductility of the protective coating. Cracking / spalling would otherwise be weak spots that could lead to corrosion.
  • the black chrome layer may contain unwanted reflections avoid helping.
  • "in the military field” means as part of a military vehicle or aircraft.
  • a connector made of aluminum is first chemically pre-nickel-plated before the protective coating according to the invention and then fed to the galvanic coating.
  • the pre-nickel-plated surface of the connector is provided with a first nickel layer in a first step of electrodeposition.
  • the first bath used in this case is based on nickel sulphate and, apart from the aqueous solution, consists exclusively of nickel, sulphate and chloride ions and boric acid.
  • the first bath is continuously filtered, even during the electrodeposition.
  • a circulation pump pumps the first bath through an activated carbon filter; the flow rate through the filter is adjusted so that the first bath circulates approximately 10 times per hour.
  • the first bath is also freed of metallic impurities with a cleaning metal part before the electrodeposition (the first layer on the connector); For this purpose, the cleaning metal part is introduced into the first bath and energized for a few hours.
  • the current density on the cleaning metal part is about 0.1 A / dm 2 .
  • the proportion of nickel ions in the first bath is around 55 g / l, the proportion of chloride ions around 26 g / l and the boric acid content around 40 g / l.
  • the galvanic deposition of the first nickel layer is then carried out at a current density of about 0.5 A / dm 2 until the first nickel layer reaches a thickness of about 15 microns Has.
  • the growth of the first nickel layer is pronounced columnar, also because the first bath has no sulfur-containing (gloss) additive.
  • the connector is removed from the first bath, then preferably rinsed with water and then fed to a second bath.
  • a nickel layer is applied, but the second bath is provided with a sulfur-containing additive, namely with saccharin.
  • the second bath consists of an aqueous solution of nickel, sulfate and chloride ions with boric acid and saccharin.
  • the proportion of nickel ions which is adjusted as in the case of the first bath via the added amount of nickel sulfate and nickel chloride, is 70 g / l in the second bath.
  • the proportion of chloride ions is 25 g / l, that of boric acid at 60 g / l, and the saccharin content is 4.5 g / l.
  • the deposition of the second nickel layer is again carried out at a current density of 0.5 A / dm 2 , up to a layer thickness of about 15 microns.
  • the connector is removed from the second bath and preferably rinsed again with water.
  • a black chromium layer with a thickness of about 1 ⁇ m is then applied as a cover layer.
  • the connector is first cathodically activated in an aqueous solution of 60 g / l sodium hydrogen sulfate at a pH of about 1.8, namely at 3 A / dm 2 for a period of 30 s.
  • the solution contains relatively small amounts of surfactants and fluorides to support the cleaning and activation function.
  • a black chromium layer known per se can be electrodeposited, namely from a bath of about 450 g / l chromic acid, about 7.5 g / l chromium sulfate, of the order of 2-8 g / l sodium or potassium carbonate or nitrate and about 1 g / l hexafluorosilicate.
  • This black chrome layer has a thickness of about 1 micron.
  • the first nickel layer is sulfur-free (sulfur content of 0 wt .-%), and the sulfur content in the second nickel layer is about 0.09 wt .-%.
  • Potential measurements on the correspondingly applied protective coating show an electrochemical potential difference between the first and the second nickel layer of around 180 mV. In a salt spray test, appropriately coated connectors show good corrosion resistance over a period of at least 1000 hours.
  • the protective coating In addition to the electrical conductivity of the protective coating distinguishes its black surface. This helps avoid light reflections, which is why the corresponding protective-coated connector can be used particularly advantageously in a military vehicle or aircraft.
  • the protective coating is relatively ductile, which helps prevent cracking or chipping.

Description

Die Erfindung betrifft das Schutzbeschichten eines Werkstücks mit Nickel.The invention relates to the protective coating of a workpiece with nickel.

Bei dem Werkstück kann es sich beispielsweise um ein metallisches Werkstück handeln, welches mit der Schutzbeschichtung vor Korrosion geschützt werden soll.The workpiece may, for example, be a metallic workpiece which is to be protected against corrosion by the protective coating.

Aus der CA 1 255 620 A1 ist ein Nickel-Schichtsystem zur Korrosionsschutzbeschichtung bekannt, bei dem auf einer inneren Nickel-Schicht mit einem reduzierten Schwefelgehalt eine schwefelhaltige Nickel-Schicht und auf dieser eine weitere Nickel-Schicht angeordnet ist. Auf dieses Drei-Schicht-System ist dann ein konventioneller Chromüberzug aufgebracht.From the CA 1 255 620 A1 is a nickel coating system for anticorrosive coating is known in which on an inner nickel layer having a reduced sulfur content, a sulfur-containing nickel layer and on this another nickel layer is arranged. On this three-layer system then a conventional chrome coating is applied.

In der US 3,528,894 A wird ein Verfahren zum Abscheiden einer Nickel-Schicht beschrieben, die unter hoher Zugspannung stehen und so einen anschließend darauf abgeschiedenen, konventionellen Chromüberzug aufreißen soll. Die Nickel-Schicht hoher Zugspannung ist Teil eines Verbunds aus drei Nickel-Schichten.In the US 3,528,894 A describes a method for depositing a nickel layer, which are under high tensile stress and so should tear a subsequently deposited on it, conventional chromium coating. The high tensile nickel layer is part of a composite of three nickel layers.

Die DE 19 900 715 A1 beschäftigt sich mit der Reinigung und Filtration von elektrolytlösungen, insbesondere mit Blick auf die Reststoffentsorgung.The DE 19 900 715 A1 deals with the cleaning and filtration of electrolyte solutions, in particular with regard to the disposal of residues.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein vorteilhaftes Verfahren zum Schutzbeschichten eines Werkstücks anzugeben.The present invention has for its object to provide an advantageous method for protective coating of a workpiece.

Erfindungsgemäß löst diese Aufgabe ein Verfahren gemäß Anspruch 1.According to the invention, this object is achieved by a method according to claim 1.

Bevorzugte Ausführungsformen finden sich in den abhängigen Ansprüchen und der vorliegenden Beschreibung, wobei in der Darstellung nicht immer im Einzelnen zwischen Verfahrens- bzw. Verwendungsaspekten und Vorrichtungsmerkmalen unterschieden wird.Preferred embodiments can be found in the dependent claims and the present description, wherein in the illustration is not always in detail between process or use aspects and device features.

Maßgeblich ist also, dass das erste Bad frei von schwefelhaltigen Zusätzen ist, was eine schwefelfreie erste Nickel-Schicht ergibt. Demgegenüber weist die dann auf dieser abgeschiedene zweite Nickel-Schicht Schwefel auf; der Erfinder hat zwischen der ersten und der zweiten Nickel-Schicht eine Potenzialdifferenz von mehr als 160 mV beobachtet.The decisive factor is therefore that the first bath is free of sulfur-containing additives, resulting in a sulfur-free first nickel layer. In contrast, the then deposited on this second nickel layer on sulfur; the inventor has observed a potential difference of more than 160 mV between the first and second nickel layers.

Diese dann noch mit der Deckschicht, einer Schwarzchromschicht, versehene Schutzbeschichtung zeigt beispielsweise in Salzsprühtests eine überraschend gute Korrosionsbeständigkeit. Entsprechend schutzbeschichtete Werkstücke können in einem Salzsprühtest sogar bis zu 1000 Stunden ausfallfrei erreichen (zum Vergleich: die Beanspruchungsstufe 3 entspricht 96 h Salzsprühtest, die Beanspruchungsstufe 4 144 h). Wie bereits eingangs erwähnt, handelt es sich bei dem Werkstück vorzugsweise um ein metallisches Werkstück, etwa aus einem Leichtmetall bzw. einer Leichtmetalllegierung, beispielsweise auf Aluminium-Basis, etwa um Aluminium, oder aus einem Eisen- bzw. Stahlwerkstoff, beispielsweise aus nicht rostfreiem Stahl. Im Allgemeinen kann das Werkstück an sich indes beispielsweise auch aus einem nicht leitenden Kunststoffmaterial vorgesehen sein, das mit einem Metallüberzug versehen ist, der dann erfindungsgemäß schutzbeschichtet wird.This then still with the top layer, a black chrome layer, provided protective coating shows, for example, in salt spray tests a surprisingly good corrosion resistance. Correspondingly protection-coated workpieces can even reach failure-free up to 1000 hours in a salt spray test (for comparison: stress level 3 corresponds to 96 hours salt spray test, stress level 4 to 144 hours). As already mentioned, the workpiece is preferably a metallic workpiece, for example of a light metal or a light metal alloy, for example based on aluminum, for example aluminum, or of an iron or steel material, for example of non-stainless steel , In general, the workpiece per se, for example, be provided from a non-conductive plastic material, which is provided with a metal coating, which is then coated according to the invention.

Sowohl die erste als auch die zweite Nickel-Schicht werden in einem Bad auf Nickelsulfat-Basis abgeschieden, es wird also jedenfalls ein Teil der Nickel-Ionen in dem Bad von Nickelsulfat (NiSO4) zur Verfügung gestellt. Das erste Bad ist frei von schwefelhaltigen Zusätzen, wobei das Sulfat außer Betracht bleibt. Das erste Bad weist also Sulfat- und Nickel-Ionen auf, jedoch von dem Sulfat abgesehen keinen weiteren schwefelhaltigen Bestandteil (ist also frei davon).Both the first and second nickel layers are deposited in a nickel sulfate-based bath, so at least some of the nickel ions in the bath of nickel sulfate (NiSO 4 ) are provided. The first bath is free of sulphurous additives, with no consideration of sulphate. Thus, the first bath has sulphate and nickel ions, but apart from the sulphate no further sulphurous constituent (so it is free).

Demgegenüber weist das zweite Bad einen schwefelhaltigen Zusatz auf, wobei das Sulfat wiederum außer Betracht bleibt. In anderen Worten weist das zweite Bad also Nickel- und Sulfat-Ionen sowie zusätzlich einen schwefelhaltigen Zusatz auf, der von dem Sulfat verschieden ist.In contrast, the second bath to a sulfur-containing additive, wherein the sulfate is again disregarded. In other words, the second one Bath so nickel and sulfate ions and in addition to a sulfur-containing additive, which is different from the sulfate.

Der Erfinder hat festgestellt, dass die entsprechend (schwefelfrei) abgeschiedene erste Nickel-Schicht eher unregelmäßig aufwächst, beispielsweise mit einer kolumnaren Struktur. Es kann also beispielsweise sein, dass sich aufgrund eines unregelmäßigen Wachstums der ersten Nickel-Schicht eine Schutzbeschichtung ergibt, die dann auch im Gesamten eine nicht ebene Oberfläche hat. Insbesondere die erste Nickel-Schicht kann von ihrer Charakteristik her nicht-einebnend sein. Dies kann zwar beispielsweise in dekorativer Hinsicht nachteilig sein, allerdings zeigt ein entsprechendes Schutzschichtsystem eben eine ausgesprochen gute Korrosionsbeständigkeil.The inventor has found that the corresponding (sulfur-free) deposited first nickel layer grows rather irregular, for example, with a columnar structure. It may be, for example, that due to a irregular growth of the first nickel layer results in a protective coating, which then has a non-planar surface as a whole. In particular, the first nickel layer may be non-planarizing in nature. Although this may be disadvantageous, for example, in decorative terms, but a corresponding protective layer system just shows a very good corrosion resistant wedge.

Das erste und das zweite Bad sind beide auf Wässer-Basis vorgesehen, es handelt sich also jeweils um eine wässrige Lösung der nachstehend weiter im Detail genannten Ionen. Soweit also vorliegend davon die Rede ist, dass ein Bad ausschließlich aus gewissen Bestandteilen besteht, bezieht sich dies auf diese Bestandteile in wässriger Lösung und wird das Wasser als Bestandteil nicht immer nochmals eigens angeführt.The first and the second bath are both provided on a water basis, so it is in each case an aqueous solution of the ions mentioned in more detail below. So far as this is the case of the fact that a bath consists exclusively of certain ingredients, this refers to these ingredients in aqueous solution and the water is not always listed as a component again.

Erfindungsgemäß wird das erste Bad, um eine entsprechend hochreine erste Nickel-Schicht zu erhalten, während der galvanischen Abscheidung (während des Aufbringens der ersten Nickel-Schicht) gefiltert, vorzugsweise mittels eines Aktivkohlefilters. So können beispielsweise organische Verunreinigungen entfernt werden. Das erste Bad wird idealerweise fortwährend durch den Filter gepumpt, vorzugsweise durch einen Filter mit Aktivkohle(platten).According to the invention, the first bath, in order to obtain a correspondingly high-purity first nickel layer, is filtered during the electrodeposition (during the application of the first nickel layer), preferably by means of an activated carbon filter. For example, organic contaminants can be removed. The first bath is ideally pumped continuously through the filter, preferably through a filter with activated charcoal (plates).

Der Durchfluss durch den Filter wird bevorzugt so gewählt, dass das erste Bad in einer Stunde mindestens 3-mal, in dieser Reihenfolge zunehmend bevorzugt mindestens 5-mal, 7-mal bzw. 9-mal, umgewälzt wird. Mögliche Obergrenzen können beispielsweise bei einem höchstens 30-, 25-, 20-, 15-, 13- bzw. 11-maligen Umwälzen pro Stunde liegen. Das "Umwälzen" meint, dass das x-fache Volumen (entsprechend dem x-maligen Umwälzen) des ersten Bades in einer Stunde durch den Filter gepumpt wird, also eben ein entsprechender Durchfluss eingestellt ist.The flow through the filter is preferably chosen such that the first bath is recirculated at least 3 times in one hour, more preferably at least 5 times, 7 times and 9 times in this order. Possible upper limits may be, for example, at a maximum of 30, 25, 20, 15, 13 or 11 revolutions per hour. The "circulating" means that the x-fold volume (corresponding to the x-times circulation) of the first bath is pumped through the filter in one hour, so just a corresponding flow is set.

Vorzugsweise werden eine Vielzahl Chargen nacheinander in dem ersten Bad beschichtet und wird das erste Bad währenddessen kontinuierlich gefiltert, vorzugsweise auch zwischen den Chargen. Je Charge können dann selbstverständlich auch mehrere Werkstücke vorgesehen sein, können also mehrere Werkstücke parallel beschichtet werden.Preferably, a plurality of batches are successively coated in the first bath, and the first bath is continuously filtered during that time, preferably also between batches. Each batch can then of course Also, several workpieces may be provided, so several workpieces can be coated in parallel.

Ebenfalls hinsichtlich einer hochreinen ersten Nickel-Schicht ist erfindungsgemäß eine Reinigung des ersten Bades vor der galvanischen Abscheidung vorgesehen, wobei ein Metallteil (als Reinigungsteil) in das erste Bad eingebracht und bestromt wird. So können beispielsweise metallische Verunreinigungen aus dem ersten Bad entfernt werden, die beispielsweise bei der Beschichtung der vorhergehenden Charge eingebracht worden sein können. Die Stromdichte auf dem Reinigungs-Metallteil beträgt vorzugsweise mindestens 0,05 A/dm2, besonders bevorzugt mindestens 0,08 A/dm2, und mögliche Obergrenzen liegen beispielsweise bei höchstens 0,2 A/dm2, vorzugsweise höchstens 0,15 A/dm2, besonders bevorzugt höchstens 0,12 A/dm2 (eine Obergrenze kann auch unabhängig von einer Untergrenze von Interesse sein, und umgekehrt).Likewise with regard to a high-purity first nickel layer, a cleaning of the first bath before the electrodeposition is provided according to the invention, wherein a metal part (as a cleaning part) is introduced into the first bath and energized. Thus, for example, metallic impurities can be removed from the first bath, which may have been introduced, for example, during the coating of the preceding batch. The current density on the cleaning metal part is preferably at least 0.05 A / dm 2 , more preferably at least 0.08 A / dm 2 , and possible upper limits are for example at most 0.2 A / dm 2 , preferably at most 0.15 A. / dm 2 , more preferably at most 0.12 A / dm 2 (an upper limit may also be independent of a lower limit of interest, and vice versa).

Diese Reinigung mit dem Reinigungs-Metallteil muss nicht vor jeder Charge erfolgen, sondern es können vorzugsweise immer eine Vielzahl Chargen nacheinander ohne Reinigung dazwischen beschichtet werden und eine Reinigung vor diesen Vielzahl Chargen und eine weitere dann danach, vor einer weiteren Vielzahl Chargen erfolgen.This cleaning with the cleaning metal part does not have to be done before each batch, but preferably a plurality of batches may be successively coated without cleaning therebetween, and a cleaning may be performed before these plurality of batches and another then afterwards before a further plurality of batches.

Vor dem Einbringen in das erste Bad wird das Werkstück in bevorzugter Ausgestaltung chemisch vorvernickelt, besonders bevorzugt ein Werkstück auf Aluminium-Basis.Before being introduced into the first bath, the workpiece is chemically pre-nickel-plated in a preferred embodiment, particularly preferably a workpiece based on aluminum.

Die erste Nickel-Schicht hat vorzugsweise eine Dicke von mindestens 5 µm, in dieser Reihenfolge zunehmend bevorzugt mindestens 6 µm, 7 µm, 8 µm, 9 µm, 10 µm, 11 µm, 12 µm bzw. 13 µm, davon unabhängige, bevorzugte Obergrenzen liegen beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 20 µm, 19 µm, 18 µm bzw. 17 µm. Das Vorsehen einer Untergrenze kann im Allgemeinen auch unabhängig vom Vorsehen einer Obergrenze offenbart sein, und umgekehrt.The first nickel layer preferably has a thickness of at least 5 μm, in this order increasingly preferably at least 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or 13 μm, of which independent, preferred upper limits For example, in this order are increasingly preferred at most 20 microns, 19 microns, 18 microns and 17 microns. The provision of a lower limit can generally also be disclosed independently of the provision of an upper limit, and vice versa.

Die zweite Nickel-Schicht hat vorzugsweise eine Dicke von mindestens 5 µm, in dieser Reihenfolge zunehmend bevorzugt mindestens 6 µm, 7 µm, 8 µm, 9 µm, 10 µm, 11 µm, 12 µm bzw. 13 µm; bevorzugte Obergrenzen liegen beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 20 µm, 19 µm, 18 µm bzw. 17 µm. Auch in diesem Fall kann das Vorsehen einer Obergrenze im Allgemeinen auch unabhängig vom Vorsehen einer Untergrenze bevorzugt sein, und umgekehrt.The second nickel layer preferably has a thickness of at least 5 μm, in this order increasingly preferably at least 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or 13 μm; preferred upper limits are for example in this order increasingly preferably at most 20 microns, 19 microns, 18 microns and 17 microns. Also in this case, the provision of an upper limit may generally be preferred independently of the provision of a lower limit, and vice versa.

In bevorzugter Ausgestaltung liegt im Falle der ersten und/oder der zweiten Nickel-Schicht die Stromdichte bei der galvanischen Abscheidung auf dem Werkstück bei mindestens 0,1 A/dm2, vorzugsweise mindestens 0,3 A/dm2, besonders mindestens 0,4 A/dm2. Vorteilhafte Obergrenzen können beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 2 A/dm2, 1,8 A/dm2, 1,6 A/dm2, 1,4 A/dm2, 1,2 A/dm2, 1 A/dm2, 0,8 A/dm2 bzw. 0,6 A/dm2 liegen. Das Vorsehen einer Obergrenze soll im Allgemeinen wiederum auch unabhängig vom Vorsehen einer Untergrenze offenbart sein, und umgekehrt.In a preferred embodiment, in the case of the first and / or the second nickel layer, the current density in the electrodeposition on the workpiece is at least 0.1 A / dm 2 , preferably at least 0.3 A / dm 2 , especially at least 0.4 A / dm 2 . Advantageous upper limits, for example, in this order increasingly preferably at most 2 A / dm 2 , 1.8 A / dm 2 , 1.6 A / dm 2 , 1.4 A / dm 2 , 1.2 A / dm 2 , 1 A / dm 2 , 0.8 A / dm 2 and 0.6 A / dm 2 are. The provision of an upper limit should again generally be disclosed independently of the provision of a lower limit, and vice versa.

In bevorzugter Ausgestaltung ist der schwefelhaltige Zusatz in dem zweiten Bad ein Glanzzusatz, also ein sogenannter Glanzbildner, wobei Saccharin als Glanzzusatz besonders bevorzugt ist. Andererseits ist das erste Bad entsprechend frei von Saccharin bzw. schwefelhaltigen Glanzzusätzen bzw. bevorzugt von Glanzzusätzen generell.In a preferred embodiment, the sulfur-containing additive in the second bath is a brightener additive, that is to say a so-called brightener, with saccharin being particularly preferred as brightener additive. On the other hand, the first bath is correspondingly free of saccharin or sulfur-containing brightener additives or preferably of brightener additives in general.

In dem zweiten Bad liegt der Glanzzusatz, vorzugsweise das Saccharin, in bevorzugter Ausgestaltung mit einer Konzentration von mindestens 2,5 g/l, vorzugsweise mindestens 3,5 g/l, besonders bevorzugt mindestens 4 g/l, vor. Vorteilhafte Obergrenzen können beispielsweise bei höchstens 15 g/l, in dieser Reihenfolge zunehmend bevorzugt höchstens 13 g/l, 11 g/l, 9 g/l, 7 g/l bzw. 6 g/l, liegen (das Vorsehen einer Obergrenze soll wiederum im Allgemeinen auch unabhängig vom Vorsehen einer Untergrenze offenbart sein, und umgekehrt).In the second bath is the brightener, preferably the saccharin, in a preferred embodiment with a concentration of at least 2.5 g / l, preferably at least 3.5 g / l, more preferably at least 4 g / l before. Advantageous upper limits may be, for example, at most 15 g / l, in this order increasingly preferably at most 13 g / l, 11 g / l, 9 g / l, 7 g / l and 6 g / l, respectively (the provision of an upper limit again generally be disclosed independently of the provision of a lower limit, and vice versa).

In dem zweiten Bad liegt die Nickel-Konzentration vorzugsweise bei mindestens 40 g/l, weiter bevorzugt bei mindestens 50 g/l bzw. 60g/l, besonders bevorzugt bei mindestens 65 g/l. Vorteilhafte Obergrenzen können beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 150 g/l, 130 g/l, 110 g/l, 90 g/l, 80 g/l bzw. 75 g/l liegen (das Vorsehen einer Obergrenze soll im Allgemeinen wiederum auch unabhängig vom Vorsehen einer Untergrenze offenbart sein, und umgekehrt). Diese Angaben beziehen sich auf die Nickel-Ionen in dem Bad, die also zumindest anteilig von dem Nickelsulfat zur Verfügung gestellt werden.In the second bath, the nickel concentration is preferably at least 40 g / l, more preferably at least 50 g / l or 60 g / l, particularly preferably at least 65 g / l. Advantageous upper limits may be, for example, in this order increasingly preferably at most 150 g / l, 130 g / l, 110 g / l, 90 g / l, 80 g / l and 75 g / l (the provision of an upper limit in general again be disclosed independently of the provision of a lower limit, and vice versa). These figures relate to the nickel ions in the bath, which are thus at least partially provided by the nickel sulfate available.

Vorzugsweise werden die Nickel-Ionen in dem zweiten Bad nicht nur durch das Nickelsulfat, sondern zusätzlich auch von Nickelchlorid (NiCl2) zur Verfügung gestellt, wobei die Chlorid-Konzentration (der Chlorid-Ionen) vorzugsweise mindestens 10 g/l, weiter bevorzugt mindestens 15 g/l, besonders bevorzugt mindestens 20 g/l, betragen soll. Vorteilhafte Obergrenzen können beispielsweise bei höchstens 50 g/l, vorzugsweise höchstens 40 g/l, besonders bevorzugt höchstens 30 g/l, liegen (das Vorsehen einer Obergrenze soll im Allgemeinen wiederum auch unabhängig vom Vorsehen einer Untergrenze offenbart sein, und umgekehrt). Vorzugsweise wird das Nickel im zweiten Bad ausschließlich durch Nickelsulfat und Nickelchlorid zur Verfügung gestellt.Preferably, the nickel ions in the second bath are provided not only by the nickel sulfate but also by nickel chloride (NiCl 2 ), wherein the chloride concentration (the chloride ion) is preferably at least 10 g / L, more preferably at least 15 g / l, more preferably at least 20 g / l should be. Advantageous upper limits may be, for example, at most 50 g / l, preferably at most 40 g / l, more preferably at most 30 g / l (the provision of an upper limit should in turn also be disclosed independently of the provision of a lower limit, and vice versa). Preferably, the nickel in the second bath is provided solely by nickel sulfate and nickel chloride.

In bevorzugter Ausgestaltung ist in dem zweiten Bad ferner Borsäure vorgesehen, und zwar vorzugsweise mit einer Konzentration von mindestens 40 g/l, weiter bevorzugt mindestens 50 g/l, besonders bevorzugt mindestens 55 g/l. Vorteilhafte Obergrenzen können beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 100 g/l, 90 g/l, 80 g/l, 70 g/l bzw. 65 g/l liegen (das Vorsehen einer Obergrenze kann im Allgemeinen wiederum auch unabhängig vom Vorsehen einer Untergrenze bevorzugt sein, und umgekehrt).In a preferred embodiment, boric acid is also provided in the second bath, preferably at a concentration of at least 40 g / l, more preferably at least 50 g / l, particularly preferably at least 55 g / l. Advantageous upper limits may be, for example, in this order increasingly preferably at most 100 g / l, 90 g / l, 80 g / l, 70 g / l and 65 g / l (the provision of an upper limit may in turn also be independent of the provision a lower limit, and vice versa).

Das zweite Bad weist also vorzugsweise Nickel-, Chlorid- und Sulfat-Ionen, Borsäure und einen Glanzzusatz, vorzugsweise Saccharin, auf. Vorzugsweise besteht das zweite Bad ausschließlich aus diesen Bestandteilen, von gegebenenfalls einem einer besseren Benetzung der zu beschichtenden Oberfläche dienenden Netzmittel abgesehen (und dem Wasser).The second bath therefore preferably has nickel, chloride and sulfate ions, boric acid and a brightener, preferably saccharin. Preferably, the second bath consists exclusively of these components, optionally one apart from a better wetting of the surface to be coated wetting agents (and the water).

In dem ersten Bad beträgt die Nickel-Konzentration vorzugsweise mindestens 40 g/l, weiter bevorzugt mindestens 45 g/l, besonders bevorzugt mindestens 50 g/l. Vorteilhafte Obergrenzen können beispielsweise bei in dieser Reihenfolge zunehmend bevorzugt höchstens 80 g/l, 70 g/l bzw. 60 g/l liegen (das Vorsehen einer Obergrenze kann im Allgemeinen auch unabhängig vom Vorsehen einer Untergrenze bevorzugt sein, und umgekehrt).In the first bath, the nickel concentration is preferably at least 40 g / l, more preferably at least 45 g / l, particularly preferably at least 50 g / l. Advantageous upper limits may be, for example, in this order increasingly preferably at most 80 g / l, 70 g / l and 60 g / l (the provision of an upper limit may generally be preferred regardless of providing a lower limit, and vice versa).

Die Chlorid-Konzentration im ersten Bad kann beispielsweise bei mindestens 10 g/l, vorzugsweise mindestens 20 g/l, besonders bevorzugt mindestens 25 g/l liegen, wobei vorteilhafte Obergrenzen (in der Reihenfolge ihrer Nennung zunehmend bevorzugt) etwa bei 50 g/l, 40 g/l bzw. 30 g/l liegen können (und im Allgemeinen das Vorsehen einer Obergrenze auch unabhängig vom Vorsehen einer Untergrenze von Interesse sein kann, und umgekehrt).The chloride concentration in the first bath may be, for example, at least 10 g / l, preferably at least 20 g / l, more preferably at least 25 g / l, with advantageous upper limits (in the order of their naming increasingly preferred) at about 50 g / l , 40 g / l and 30 g / l respectively (and in general the provision of an upper limit may also be of interest irrespective of the provision of a lower limit, and vice versa).

In dem ersten Bad liegt die Konzentration an Borsäure bei vorzugsweise mindestens 20 g/l, weiter bevorzugt mindestens 30 g/l, besonders bevorzugt mindestens 35 g/l, wobei vorteilhafte Obergrenzen (in der Reihenfolge ihrer Nennung zunehmend bevorzugt) etwa bei höchstens 70 g/l, 60 g/l, 50 g/l bzw. 45 g/l liegen (und das Vorsehen einer Obergrenze wiederum auch unabhängig vom Vorsehen einer Untergrenze von Interesse sein kann, und umgekehrt). Von dem Wasser der wässrigen Lösung und gegebenenfalls einem (schwefelfreien) Netzmittel abgesehen besteht das zweite Bad vorzugsweise ausschließlich aus Nickel-, Sulfat- sowie Chlorid-Ionen und der Borsäure.In the first bath, the concentration of boric acid is preferably at least 20 g / l, more preferably at least 30 g / l, more preferably at least 35 g / l, with favorable upper limits (in the order of their nomination increasingly preferred) about at most 70 g / l, 60 g / l, 50 g / l and 45 g / l respectively (and the provision of an upper limit may again be of interest irrespective of the provision of a lower limit, and vice versa). Apart from the water of the aqueous solution and optionally a (sulfur-free) wetting agent, the second bath is preferably composed exclusively of nickel, sulfate and chloride ions and boric acid.

Die in bevorzugter Ausgestaltung als Deckschicht vorgesehene Schwarzchromschicht hat vorzugsweise eine Dicke von mindestens 0,5 µm und von höchstens 1,5 µm (die Obergrenze kann wiederum unabhängig von der Untergrenze von Interesse sein, und umgekehrt). Soweit generell in der vorliegenden Offenbarung von Schichtdicken die Rede ist, beziehen sich diese jeweils auf die fertige Schicht, also die Schichtdicke am Ende / nach der Abscheidung (also nicht auf eine zwischenzeitliche Dicke während der Abscheidung). Die Dicke wird senkrecht zur Oberfläche des Werkstücks genommen, und im Falle einer Schicht mit über die Oberfläche des Werkstücks variierender Dicke wird ein Mittelwert betrachtet.The black chromium layer provided in a preferred embodiment as a cover layer preferably has a thickness of at least 0.5 μm and of at most 1.5 μm (the upper limit may in turn be independent of the lower limit of interest, and vice versa). Insofar as layer thicknesses are generally referred to in the present disclosure, these relate in each case to the finished layer, ie the layer thickness at the end / after the deposition (ie not at an intermediate thickness during the deposition). The thickness is taken perpendicular to the surface of the workpiece, and in the case of a layer having varying thickness over the surface of the workpiece, an average value is considered.

Wenngleich im Allgemeinen auf die Deckschicht auch noch eine weitere Schicht aufgebracht werden könnte, handelt es sich dabei vorzugsweise um die abschließende Schicht, also die Schicht, die dann die Außenoberfläche des schutzbeschichteten Werkstücks bildet.Although a further layer could generally also be applied to the cover layer, this is preferably the final layer, ie the layer which then forms the outer surface of the protective-coated workpiece.

Die Erfindung betrifft auch ein entsprechend schutzbeschichtetes Werkstück, also ein Werkstück mit einer ersten Nickel-Schicht, einer zweiten Nickel-Schicht auf der ersten Nickel-Schicht (welche an die erste Nickel-Schicht grenzt) und einer Deckschicht auf der zweiten Nickel-Schicht (welche an die zweite Nickel-Schicht grenzt). Die erste Nickel-Schicht ist dabei frei von Schwefel, wohingegen die zweite Nickel-Schicht einen Massenanteil von mindestens 0,05 Gew.-%, vorzugsweise mindestens 0,07 Gew.-%, besonders bevorzugt mindestens 0,08 Gew.-%, hat. Mögliche Obergrenzen liegen beispielsweise bei höchstens 0,15 Gew.-%, vorzugsweise höchstens 0,12 Gew.-%, besonders bevorzugt höchstens 0,1 Gew.-%.The invention also relates to a correspondingly protective-coated workpiece, that is to say a workpiece having a first nickel layer, a second nickel layer on the first nickel layer (which adjoins the first nickel layer) and a cover layer on the second nickel layer (US Pat. which adjoins the second nickel layer). The first nickel layer is free of sulfur, whereas the second nickel layer has a mass fraction of at least 0.05 wt .-%, preferably at least 0.07 wt .-%, particularly preferably at least 0.08 wt .-%, Has. Possible upper limits are for example at most 0.15 wt .-%, preferably at most 0.12 wt .-%, particularly preferably at most 0.1 wt .-%.

Diese Angaben den Schwefelgehalt betreffend sollen ausdrücklich auch hinsichtlich der Verfahrenskategorie offenbart sein, also dahingehend, dass eine erste Nickel-Schicht abgeschieden wird, die frei von Schwefel ist und eine zweite Nickel-Schicht abgeschieden wird, die einen entsprechenden Mindestgehalt an Schwefel aufweist (und vorzugsweise auch einen vorliegend offenbarten Maximalgehalt). Andererseits betrifft die Erfindung eben ausdrücklich auch ein Werkstück, das in einem vorliegend offenbarten Verfahren schutzbeschichtet wurde.This information regarding sulfur content should also be expressly disclosed with regard to the process category, that is, a first nickel layer which is free of sulfur and a second nickel layer is deposited, which has a corresponding minimum sulfur content (and preferably also a maximum content disclosed herein). On the other hand, the invention also expressly relates to a workpiece that has been protective coated in a method disclosed herein.

Für ein entsprechendes Schichtsystem, in dem also die erste Nickel-Schicht tatsächlich frei von Schwefel ist (also nicht bloß nur eine geringe Menge an Schwefel aufweist, sondern tatsächlich keinen Schwefel), die darauf angeordnete zweite Nickel-Schicht jedoch schwefelhaltig ist, hat der Erfinder eine vergleichsweise große elektrochemische Potenzialdifferenz zwischen den beiden Nickel-Schichten beobachtet. Diese beträgt mindestens 160 mV, vorzugsweise mindestens 170 mV, wobei mögliche Obergrenzen beispielsweise bei höchstens 260 mV, 240 mV, 220 mV, 200 mV bzw. 190 mV liegen können. Vorzugsweise besteht die erste Nickel-Schicht ausschließlich aus Nickel.For a corresponding layer system, in which therefore the first nickel layer is actually free of sulfur (ie, not only has only a small amount of sulfur, but actually no sulfur), but the second nickel layer arranged thereon contains sulfur, the inventor has a comparatively observed large electrochemical potential difference between the two nickel layers. This is at least 160 mV, preferably at least 170 mV, with possible upper limits, for example, at most 260 mV, 240 mV, 220 mV, 200 mV or 190 mV can be. Preferably, the first nickel layer consists exclusively of nickel.

Diese großen Potenzialdifferenz korrespondiert mit der beobachteten guten Korrosionsbeständigkeit. Letztere wird auch durch die bevorzugt als Abdeckschicht vorgesehene Schwarzchrom-Schicht nicht beeinträchtigt, gegebenenfalls sogar noch ein Stück weit verbessert. Ein besonderer Vorteil dieser Schutzbeschichtung (mit vorzugsweise elektrolytisch abgeschiedenem Schwarzchrom als Deckschicht) besteht also darin, dass sie einerseits gut vor Korrosion schützt und andererseits elektrisch leitend ist.This large potential difference corresponds with the observed good corrosion resistance. The latter is not impaired by the black chromium layer, which is preferably provided as a cover layer, and may even be improved to some extent. A particular advantage of this protective coating (preferably with electrolytically deposited black chrome as the cover layer) is that it protects against corrosion on the one hand and is electrically conductive on the other hand.

Auch vor diesem Hintergrund handelt es sich bei dem Werkstück in bevorzugter Ausgestaltung um ein elektrisches Verbindungsteil, das schraub- und/oder steckbar ist, also beispielsweise um einen Steckverbinder für etwa eine Strom- und/oder Datenleitung. Der Erfinder hat festgestellt, dass die Schutzbeschichtung vergleichsweise duktil ist, was einer Rissbildung und einem Abplatzen vorbeugen helfen kann. Nach momentanen Kenntnisstand ist dies zumindest auch auf die hochrein abgeschiedene erste Nickel-Schicht zurückzuführen. Bei einem Steckverbinder, der auch verschraubt wird, kann das Gewinde den mechanisch am stärksten beanspruchten Bereich darstellen. Bei einem Test an einem solchen Steckverbinder war die Schutzbeschichtung auch dort nach 500-maligen Schraubverbinden und Lösen noch intakt, was auch auf die hohe Duktilität der Schutzbeschichtung zurückzuführen ist. Eine Rissbildung / ein Abplatzen wären anderenfalls Schwachstellen, die zu einer Korrosion führen könnten.Even with this background, the workpiece in a preferred embodiment is an electrical connection part that can be screwed and / or plugged in, that is, for example, a connector for a power and / or data line. The inventor has found that the protective coating is relatively ductile, which can help prevent cracking and spalling. According to current knowledge, this is at least attributable to the highly pure deposited first nickel layer. In a connector that is also bolted, the thread can represent the most mechanically stressed area. In a test on such a connector, the protective coating was also there after 500-times Schraubverbinden and loosening still intact, which is also due to the high ductility of the protective coating. Cracking / spalling would otherwise be weak spots that could lead to corrosion.

Auch aufgrund der schwarzen bzw. in allgemeineren Worten dunklen Oberfläche der bevorzugten Schwarzchromschicht liegen bevorzugte Verwendungen im Militärbereich. Die Schwarzchromschicht kann beispielsweise ungewünschte Reflexionen vermeiden helfen. "Im Militärbereich" meint beispielsweise als Teil eines Militärfahrzeugs oder -flugzeugs.Also, due to the black or more generally dark surface of the preferred black chrome layer, preferred uses are in the military field. For example, the black chrome layer may contain unwanted reflections avoid helping. For example, "in the military field" means as part of a military vehicle or aircraft.

Im Folgenden wird die Erfindung anhand eines Ausführungsbeispiels näher erläutert, wobei die einzelnen Merkmale auch in anderer Kombination erfindungswesentlich sein können und in dieser Form offenbart sein sollen.In the following, the invention will be explained in more detail with reference to an embodiment, wherein the individual features may be essential to the invention in another combination and should be disclosed in this form.

Ein aus Aluminium gefertigter Steckverbinder wird vor dem erfindungsgemäßen Schutzbeschichten zunächst chemisch vorvernickelt und dann der galvanischen Beschichtung zugeführt.A connector made of aluminum is first chemically pre-nickel-plated before the protective coating according to the invention and then fed to the galvanic coating.

Bei dieser wird die vorvernickelte Oberfläche des Steckverbinders in einem ersten Schritt galvanischer Abscheidung mit einer ersten Nickel-Schicht versehen. Das dabei verwendete erste Bad ist auf Nickelsulfat-Basis vorgesehen und besteht, von der wässrigen Lösung abgesehen, ausschließlich aus Nickel-, Sulfat- sowie Chlorid-Ionen und Borsäure.In this case, the pre-nickel-plated surface of the connector is provided with a first nickel layer in a first step of electrodeposition. The first bath used in this case is based on nickel sulphate and, apart from the aqueous solution, consists exclusively of nickel, sulphate and chloride ions and boric acid.

Um die Reinheit zu gewährleisten, wird das erste Bad kontinuierlich gefiltert, auch während der galvanischen Abscheidung. Eine Umwälzpumpe pumpt das erste Bad durch einen Aktivkohlefilter; die Durchflussurate durch den Filter ist so eingestellt, dass das erste Bad pro Stunde ca. 10-mal umgewälzt wird. Ferner wird das erste Bad vor der galvanischen Abscheidung (der ersten Schicht auf den Steckverbinder) auch mit einem Reinigungs-Metallteil von metallischen Verunreinigungen befreit; dazu wird das Reinigungs-Metallteil in das erste Bad eingebracht und für einige Stunden bestromt. Die Stromdichte auf dem Reinigungs-Metallteil liegt bei ca. 0,1 A/dm2.To ensure the purity, the first bath is continuously filtered, even during the electrodeposition. A circulation pump pumps the first bath through an activated carbon filter; the flow rate through the filter is adjusted so that the first bath circulates approximately 10 times per hour. Furthermore, the first bath is also freed of metallic impurities with a cleaning metal part before the electrodeposition (the first layer on the connector); For this purpose, the cleaning metal part is introduced into the first bath and energized for a few hours. The current density on the cleaning metal part is about 0.1 A / dm 2 .

Der Anteil an Nickel-Ionen im ersten Bad liegt bei rund 55 g/l, der Anteil an Chlorid-Ionen bei rund 26 g/l und der Anteil der Borsäure bei rund 40 g/l. Die galvanische Abscheidung der ersten Nickel-Schicht erfolgt dann bei einer Stromdichte von ca. 0,5 A/dm2 bis die erste Nickel-Schicht eine Dicke von ca. 15 µm erreicht hat. Das Wachstum der ersten Nickel-Schicht ist ausgeprägt kolumnar, auch weil das erste Bad keinen schwefelhaltigen (Glanz) Zusatz aufweist.The proportion of nickel ions in the first bath is around 55 g / l, the proportion of chloride ions around 26 g / l and the boric acid content around 40 g / l. The galvanic deposition of the first nickel layer is then carried out at a current density of about 0.5 A / dm 2 until the first nickel layer reaches a thickness of about 15 microns Has. The growth of the first nickel layer is pronounced columnar, also because the first bath has no sulfur-containing (gloss) additive.

Nach dem Aufbringen der ersten Nickel-Schicht wird der Steckverbinder aus dem ersten Bad genommen, dann vorzugsweise mit Wasser gespült und anschließend einem zweiten Bad zugeführt. Auch im zweiten galvanischen Schritt wird eine Nickel-Schicht aufgebracht, allerdings ist das zweite Bad mit einem schwefelhaltigen Zusatz versehen, nämlich mit Saccharin. Das zweite Bad besteht aus einer wässrigen Lösung von Nickel-, Sulfat- und Chlorid-Ionen mit Borsäure und Saccharin. Der Anteil an Nickel-Ionen, der wie im Falle des ersten Bads auch über die zugegebene Menge an Nickelsulfat und Nickelchlorid eingestellt wird, beträgt beim zweiten Bad 70 g/l. Der Anteil der Chlorid-Ionen liegt bei 25 g/l, jener der Borsäure bei 60 g/l, und der Saccharin-Anteil liegt bei 4,5 g/l.After the application of the first nickel layer, the connector is removed from the first bath, then preferably rinsed with water and then fed to a second bath. Also in the second galvanic step, a nickel layer is applied, but the second bath is provided with a sulfur-containing additive, namely with saccharin. The second bath consists of an aqueous solution of nickel, sulfate and chloride ions with boric acid and saccharin. The proportion of nickel ions, which is adjusted as in the case of the first bath via the added amount of nickel sulfate and nickel chloride, is 70 g / l in the second bath. The proportion of chloride ions is 25 g / l, that of boric acid at 60 g / l, and the saccharin content is 4.5 g / l.

Die Abscheidung der zweiten Nickel-Schicht erfolgt wiederum bei einer Stromdichte von 0,5 A/dm2, und zwar bis zu einer Schichtdicke von ca. 15 µm.The deposition of the second nickel layer is again carried out at a current density of 0.5 A / dm 2 , up to a layer thickness of about 15 microns.

Anschließend wird der Steckverbinder aus dem zweiten Bad genommen und vorzugsweise nochmals mit Wasser gespült. In einem letzten Schritt wird dann eine Schwarzchromschicht mit einer Dicke von rund 1 µm als Deckschicht aufgebracht. Dazu wird der Steckverbinder zunächst in einer wässrigen Lösung von 60 g/l Natriumhydrogensulfat bei einem pH-Wert von etwa 1,8 kathodisch aktiviert, und zwar bei 3 A/dm2 für eine Zeit von 30 s. Die Lösung enthält dabei relativ geringe Mengen an Tensiden und Fluoriden zur Unterstützung der Reinigungs- und Aktivierungsfunktion.Subsequently, the connector is removed from the second bath and preferably rinsed again with water. In a last step, a black chromium layer with a thickness of about 1 μm is then applied as a cover layer. For this purpose, the connector is first cathodically activated in an aqueous solution of 60 g / l sodium hydrogen sulfate at a pH of about 1.8, namely at 3 A / dm 2 for a period of 30 s. The solution contains relatively small amounts of surfactants and fluorides to support the cleaning and activation function.

Daraufhin kann eine an sich bekannte Schwarzchromschicht elektrolytisch abgeschieden werden, und zwar aus einem Bad von etwa 450 g/l Chromsäure, etwa 7,5 g/l Chromsulfat, in der Größenordnung von 2 - 8 g/l Natrium- oder Kaliumcarbonat oder -nitrat und etwa 1 g/l Hexafluorosilikat. Diese Schwarzchromschicht hat eine Stärke von etwa 1 µm.Thereafter, a black chromium layer known per se can be electrodeposited, namely from a bath of about 450 g / l chromic acid, about 7.5 g / l chromium sulfate, of the order of 2-8 g / l sodium or potassium carbonate or nitrate and about 1 g / l hexafluorosilicate. This black chrome layer has a thickness of about 1 micron.

Die erste Nickel-Schicht ist schwefelfrei (Schwefelanteil von 0 Gew.-%), und der Schwefelanteil in der zweiten Nickel-Schicht beträgt rund 0,09 Gew.-%. Potenzialmessungen an der entsprechend aufgebrachten Schutzbeschichtung zeigen eine elektrochemische Potenzialdifferenz zwischen der ersten und der zweiten Nickel-Schicht von rund 180 mV. In einem Salzsprühtest zeigen entsprechend schutzbeschichtete Steckverbinder eine gute Korrosionsbeständigkeit über einen Zeitraum von mindestens 1000 Stunden.The first nickel layer is sulfur-free (sulfur content of 0 wt .-%), and the sulfur content in the second nickel layer is about 0.09 wt .-%. Potential measurements on the correspondingly applied protective coating show an electrochemical potential difference between the first and the second nickel layer of around 180 mV. In a salt spray test, appropriately coated connectors show good corrosion resistance over a period of at least 1000 hours.

Neben der elektrischen Leitfähigkeit zeichnet die Schutzbeschichtung ihre schwarze Oberfläche aus. Dies hilft Lichtreflexe vermeiden, weswegen der entsprechend schutzbeschichtete Steckverbinder besonders vorteilhaft in einem Militärfahrzeug oder -flugzeug eingesetzt werden kann. Die Schutzbeschichtung ist vergleichsweise duktil, was einer Rissbildung bzw. einem Abplatzen vorbeugen hilft.In addition to the electrical conductivity of the protective coating distinguishes its black surface. This helps avoid light reflections, which is why the corresponding protective-coated connector can be used particularly advantageously in a military vehicle or aircraft. The protective coating is relatively ductile, which helps prevent cracking or chipping.

Claims (13)

  1. A method for protectively coating a workpiece, comprising the following steps in the order mentioned
    - applying a first nickel layer by a galvanic deposition in a first bath based on nickel; sulfate, which contains, apart from the sulfate, no sulphurous additives;
    - applying a second nickel layer which contacts said first nickel layer, wherein said second nickel layer is applied by a galvanic deposition in a second bath based on nickel sulfate, which contains, apart from the sulfate, a sulphurous additive;
    - applying a chrome layer as a cover layer, which contacts said second nickel layer,
    characterized in that
    said chrome layer is a black chrome layer and that said first bath is cleaned prior to said galvanic deposition by adding a metal part and applying a current to it, wherein said first bath is further filtered during said galvanic deposition.
  2. The method according to claim 1, wherein said first bath is filtered during said galvanic deposition by an activated carbon filter.
  3. The method according to claim 1 or 2, wherein at least one of said first nickel layer and said second nickel layer has a thickness of at least 5 µm and not more than 20 µm.
  4. The method according to one of the preceding claims, wherein a current density on said workpiece during said galvanic deposition of at least one of said first nickel layer and said second nickel layer is at least 0,1 A/dm2 and not more than 2 A/dm2.
  5. The method according to one of the preceding claims, wherein said sulphurous additive in said second bath is a brightener.
  6. The method according to claim 5, wherein said brightener is saccharin.
  7. The method according to claim 5 or 6, wherein said brightener has a concentration of at least 2,5 g/l and not more than 15 g/l in said second bath.
  8. The method according to one of the preceding claims, wherein said second bath contains nickel in a concentration of at least 40 g/l and not more than 150 g/l.
  9. The method according to one of the preceding claims, wherein said second bath contains chloride in a concentration of at least 10 g/l and not more than 50 g/l.
  10. The method according to one of the preceding claims, wherein said second bath contains boric acid in a concentration of at least 40 g/l and not more than 100 g/l.
  11. A workpiece which has been protectively coated in a method according to one of the preceding claims, namely which is coated by
    - a first nickel layer of galvanic nickel, which contains no sulphur
    - a second nickel layer of galvanic nickel on said first nickel layer, which contacts said first nickel layer, wherein sat second nickel layer contains sulphur with a mass portion of at least 0,05 weight percent
    - a black chrome layer as a cover layer on top of said second nickel layer, which contacts said second nickel layer,
    wherein, in said workpiece, an electrochemical potential difference between said first nickel layer and said second nickel layer is at least 160 mV.
  12. The workpiece according to claim 11, which is an electrical connection part being at least one of screwable and pluggable.
  13. A use of the workpiece according to one of claims 11 and 12 in the military sector.
EP14177678.1A 2014-07-18 2014-07-18 Method for providing a workpiece with a protective coating Not-in-force EP2975162B1 (en)

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Publication number Priority date Publication date Assignee Title
FR1447970A (en) * 1964-10-12 1966-08-05 Renault Corrosion resistant decorative chrome deposits
US3528894A (en) * 1966-08-25 1970-09-15 M & T Chemicals Inc Method of electrodepositing corrosion resistant coating
US3795591A (en) * 1972-07-03 1974-03-05 Oxy Metal Finishing Corp Electrodeposition of bright nickel iron deposits employing a compound containing a sulfide and a sulfonate
AU563637B2 (en) * 1984-04-20 1987-07-16 Omi International Corp. Electrodepositing composite nickel layers
CN1021237C (en) * 1991-05-14 1993-06-16 沈阳电镀厂 Nickle electric-plating method of rare earth permanent magnetic body
DE19900715A1 (en) * 1999-01-11 2000-07-13 Henry Bergmann Electrochemical treatment of aluminum-containing solution, e.g. spent aluminum surface treatment or rinsing solution, comprises electrolysis and electrodialysis in a divided cell containing a precious metal, oxide and/or mixed oxide anode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Praktische Oberflächentechnik", 1 January 1996, VIEWEG+TEUBNER VERLAG, Wiesbaden, ISBN: 978-3-322-86118-4, article KLAUS-PETER MÜLLER: "Praktische Oberflächentechnik", pages: 341 - 345, XP055320301, DOI: 10.1007/978-3-322-86118-4 *

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