EP2451997A1 - Nickel system - Google Patents

Nickel system

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Publication number
EP2451997A1
EP2451997A1 EP10742444A EP10742444A EP2451997A1 EP 2451997 A1 EP2451997 A1 EP 2451997A1 EP 10742444 A EP10742444 A EP 10742444A EP 10742444 A EP10742444 A EP 10742444A EP 2451997 A1 EP2451997 A1 EP 2451997A1
Authority
EP
European Patent Office
Prior art keywords
nickel
electrolyte according
nickel electrolyte
layers
acid
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.)
Granted
Application number
EP10742444A
Other languages
German (de)
French (fr)
Other versions
EP2451997B1 (en
Inventor
Andreas Prinz
Heiko Viecenz
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.)
HSO Herbert Schmidt GmbH and Co KG
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Herbert Schmidt GmbH and Co KG
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Application filed by Herbert Schmidt GmbH and Co KG filed Critical Herbert Schmidt GmbH and Co KG
Priority to EP10742444.2A priority Critical patent/EP2451997B1/en
Publication of EP2451997A1 publication Critical patent/EP2451997A1/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
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y10T428/12667—Oxide of transition metal or Al

Definitions

  • the present invention relates to a nickel electrolyte and its use.
  • Galvanic nickel electrolytes are known to the person skilled in the art in various designs.
  • components are provided with copper layers for the surface finishing, the layers with typically two or three nickel ⁇ and a layer of chromium or other alloys are provided. While the outer layers serve the visual appearance of the component, the lower layers essentially serve as corrosion protection.
  • Typical applications are, for example, panels, strips, condenser ⁇ protective grids on automobiles.
  • nickel electrolytes are based on what is known as Watts 's electrolyte, which typically has the following composition:
  • nickel layers are essentially made up of microcracked and microporous layers.
  • microcracked layers the deposition of nickel by the use of organic acids creates stresses. A micrograph of such a layer is shown in FIG. The cracks in the nickel layer continue in the chromium deposited thereon. Corrosive attacks are thereby transmitted from the outer chromium layer to the inner nickel layer and do not affect the surface.
  • Microporous layers have displaced the microcracked layers in many areas. In microporous layers in addition to sulfur compounds and solids are used, but no organic acids.
  • FIG. 4 shows a photograph of a microporous layer.
  • No. 3,471,271 describes a process in which cracks are produced in the nickel layer by adding large amounts of solids.
  • the object of the present invention was to provide nickel electrolytes with which coatings with other, preferably improved, corrosion properties can be obtained.
  • Suitable nickel compounds are various nickel salts, in particular nickel chloride, nickel acetate, nickel sulfate and mixtures thereof.
  • the amount of nickel in the nickel electrolyte is preferably 5 to 300 g / L, with an amount of 200 to 280 g / L, each calculated to NiCl, being preferred.
  • Particularly suitable organic acids are low molecular weight organic acids such as formic acid, acetic acid, propionic acid, butyric acid and about this. Suitable amounts of the acid are about 5 to 150 g / l, preferably 10 to 30 g / l or 40 to 70 g / l.
  • the nickel electrolyte according to the invention contains an inorganic solid, for example aluminum oxide, silicon dioxide, silicates such as, for example, talc, silicon carbide or mixtures thereof.
  • Preferred contents of the inorganic solid are in the range of 0.1 to 0.8 g / l, with an amount of 0.1 to 0.3 g / l being preferred.
  • the nickel electrolyte preferably contains more than 0.1 g / l of solids, for example 0.15 g / l or 0.2 g / l.
  • the nickel electrolyte contains less than 0.8 g / L or less than 0.7 g / L, more preferably less than 0.5 g / L, and more preferably less than 0.4 g / L or less than 0.3 g / l.
  • the amount of inorganic solids may also be 0.05 g / L to 100 g / L or 0.1 to 60 g / L.
  • average particle size of the inorganic solid (d50) preference is given to using particle sizes of from 0.1 to 3 ⁇ m, more preferably from 0.8 to 3 ⁇ m, even more preferably from 1 to 2.2 ⁇ m.
  • the mean grain size may be in the range of 200 nm to 5 ⁇ m or 0.8 to 3 ⁇ m.
  • inorganic particles are incorporated in the layer.
  • the result is a microcracked layer containing embedded inorganic particles.
  • the corresponding layers obtained have hitherto not been known to the person skilled in the art.
  • the nickel electrolyte may contain conventional further ingredients of electrolytes, in particular wetting agents, buffer substances and / or brighteners. In one embodiment, the nickel electrolyte additionally contains ammonia. In one embodiment of the invention, the nickel electrolyte according to the invention contains no boric acid. It is preferred that the content of boric acid is ⁇ 10 g / L, more preferably ⁇ 5 g / L, even more preferably ⁇ 1 g / L.
  • the nickel electrolyte according to the invention contains no reducing agent such as hypophosphite, as it is used for electroless deposition.
  • the content of reducing agent is preferably ⁇ 10 g / l, more preferably ⁇ 5 g / l, even more preferably ⁇ 1 g / l.
  • Reducing agent is a means that can reduce Ni 2+ from Ni to Ni.
  • the nickel electrolyte according to the invention is preferably adjusted to an acidic pH between pH 1.5 and 6.5, more preferably 2 to 5, and even more preferably 3 to 4.5. This can be done in the usual way by adding acids or alkalis.
  • the invention also provides a process for electroplating a component comprising the step of contacting the component with the nickel electrolyte according to the invention and applying a current density of 2 to 15, preferably 5 to 10 A / dm 2 at a temperature of 20 to 55, preferably 25 to 35 ° C.
  • a nickel electrolyte is used which already leads to a microcracked structure without the addition of solid, regardless of how the further treatment of the electrolyte is carried out, for example whether the further treatment of the layer involves hot or cold rinsing.
  • Layer thicknesses of more than 2 ⁇ m up to 5 ⁇ m are particularly preferred.
  • the chrome layer thickness shows less influence.
  • Chromium layer thicknesses in the range of about 0.375 to 2 microns are suitable.
  • Electroplating with nickel electrolytes is known in principle to a person skilled in the art and customary process measures for plating with nickel electrolytes are also applicable to the novel electrolyte according to the invention.
  • the new electrolyte By using the new electrolyte, a special structure is obtained which has defined pores and cracks. Surprisingly, this leads to a significant change in the corrosion properties.
  • the component being electroplated is plastic or metal.
  • one or more copper layers are applied, which are then coated by one or more nickel layers and finally by decorative layers, for example chrome layers.
  • At least one of the nickel layers is a nickel layer according to the invention.
  • the nickel electrolyte according to the invention can advantageously be applied with conventional galvanic equipment, so that no structural measures are required.
  • the invention furthermore relates to a component which has one or more layers obtainable by the process according to the invention.
  • FIG. 1 shows the results of a CASS test with components coated according to Comparative Example 1 (back) and Comparative Example 2 (front).
  • Figure 2 shows results of a test against calcium chloride salts based on kaolin pastes. A component with a coating according to Example 2 (top) with a coating according to Comparative Example 1 (bottom) was compared.
  • FIG. 3 shows a photograph of a microcracked layer of the prior art.
  • Figure 4 shows a microporous layer according to the prior art.
  • Figure 5 shows a structure obtained with the nickel electrolyte of the present invention.
  • FIG. 6 shows a surface image obtained with that of the electrolyte according to the invention, but without the addition of an inorganic solid.
  • FIG. 7 shows a scanning electron micrograph without solids of the surface according to FIG. 6.
  • FIG. 8 shows a scanning electron micrograph of the layers according to the invention with a built-in solid.
  • FIG. 9 shows a coating as obtained with an electrolyte of US Pat. No. 3,471,271 Example 1 (without addition of solid).
  • FIG. 10 shows, under identical conditions, the deposition of an electrolyte according to the invention according to Example 2 (without addition of solid).
  • the layers according to the invention show improved corrosion resistance, in particular in the corrosion of calcium chloride as road salt.
  • Calcium chloride has a lower dew point than other salts and is extremely active due to its strong hyposcopic behavior.
  • the widespread microporous chromium coatings are often attacked clearly visible already after a winter.
  • Nickel chloride 45 g / l
  • Brightening additive 0.5 ml / l
  • the coating produced shows a solids-dependent microporous surface with at least 8,000 pores / cm 2 .
  • Nickel chloride 250 g / l
  • Brightening additive 1 ml / l
  • the coating shows a defined, coherent structure combination with increased surface area and micropores.
  • Nickel chloride 180 g / l
  • Brightening additive 0.5 ml / l
  • Nickel chloride 210 g / l
  • Nickel sulfate 44 g / l
  • Brightening additive 1.0 ml / l
  • the coating shows a defined, coherent structure combination with an enlarged surface area and micropores.
  • CASS test copper accelerated acidic salt spray test
  • DIN 50021 The CASS test (copper accelerated acidic salt spray test) is described in DIN 50021.
  • test pieces are sprayed with a saline solution of the following composition: - 50 g / l sodium chloride
  • the part is removed from the mist, rinsed thoroughly and dried.
  • the dissolved copper salt causes a dissolution of the least noble metal in the layer system.
  • the CASS test shows the corrosion path in the layer system.
  • Figure 1 shows the results of the CASS test after 96 h.
  • the rear component, coated according to Comparative Example 1 shows corrosion phenomena can be seen, while the component with a coating according to Example 2 (front) shows no signs of corrosion.
  • a paste is prepared from 5 ml of saturated calcium chloride solution and 3 g of kaolin and a pH of 6.5 to 7.5. It is a mushy substance. A defined amount is applied to a sample body in a suitable diameter and stored at 60 0 C for 48 h. This is an accelerated test for assessing resistance to calcium chloride-containing road salt.
  • FIG. 2 shows that the component coated in accordance with Comparative Example 1 (front) shows marked traces of corrosion, while the part coated according to the invention (rear) shows no signs of corrosion.
  • FIG. 9 shows that the structure has no cracks without addition of solid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention relates to a nickel electrolyte containing: nickel salts; organic acid or the salts thereof; 0.05 to 1 g/l inorganic solid matter with a grain size (d50) of 0.1 to 3 μm.

Description

Nickelsvstem  Nickelsvstem
Die vorliegende Erfindung betrifft einen Nickelelektrolyten und seine Verwendung . The present invention relates to a nickel electrolyte and its use.
Galvanische Nickelelektrolyte sind dem Fachmann in verschiedensten Ausfüh- rungen bekannt. Beispielsweise werden zur Oberflächenveredelung Bauteile mit Kupferschichten versehen, die mit typischerweise zwei oder drei Nickel¬ schichten und einer Chromschicht oder anderen Legierungen versehen werden. Während die äußeren Schichten dem optischen Erscheinungsbild des Bauteils dient, dienen die unteren Schichten im Wesentlichen dem Korrosions- schütz. Galvanic nickel electrolytes are known to the person skilled in the art in various designs. For example, components are provided with copper layers for the surface finishing, the layers with typically two or three nickel ¬ and a layer of chromium or other alloys are provided. While the outer layers serve the visual appearance of the component, the lower layers essentially serve as corrosion protection.
Typische Anwendungsbereiche sind beispielsweise Blenden, Leisten, Kühler¬ schutzgitter an Automobilen. Typical applications are, for example, panels, strips, condenser ¬ protective grids on automobiles.
Die am häufigsten verwendeten Nickelelektrolyten beruhen auf dem sogenannten Watts 'sehen Elektrolyten, der typischerweise die folgende Zusam- mensetzung hat: The most commonly used nickel electrolytes are based on what is known as Watts 's electrolyte, which typically has the following composition:
- NiSO4• 7 H2O 240 bis 310 g/l - NiSO 4 • 7H 2 O 240 to 310 g / l
- NiCI2• 6 H2O 45 bis 50 g/l - NiCl 2 • 6 H 2 O between 45 and 50 g / l
- H3BO3 30 bis 40 g/l. - H 3 BO 3 30 to 40 g / l.
Zum Korrosionsschutz werden bei Nickelschichten im Wesentlichen mikrorissi- ge und mikroporige Schichten eingesetzt. Bei mikrorissigen Schichten werden beim Abscheiden des Nickels durch den Einsatz organischer Säuren Spannungen erzeugt. Eine Mikroskopaufnahme einer solchen Schicht ist in Figur 3 gezeigt. Die Risse in der Nickelschicht setzen sich im darauf abgeschiedenen Chrom fort. Korrosionsangriffe werden hierdurch von der äußeren Chrom- schicht auf die innere Nickelschicht weitergegeben und beeinträchtigen die Oberfläche nicht. Mikroporige Schichten haben in vielen Bereichen die mikrorissigen Schichten verdrängt. Bei mikroporigen Schichten werden neben Schwefelverbindungen auch Feststoffe eingesetzt, allerdings keine organischen Säuren. For corrosion protection, nickel layers are essentially made up of microcracked and microporous layers. For microcracked layers, the deposition of nickel by the use of organic acids creates stresses. A micrograph of such a layer is shown in FIG. The cracks in the nickel layer continue in the chromium deposited thereon. Corrosive attacks are thereby transmitted from the outer chromium layer to the inner nickel layer and do not affect the surface. Microporous layers have displaced the microcracked layers in many areas. In microporous layers in addition to sulfur compounds and solids are used, but no organic acids.
Figur 4 zeigt eine Aufnahme einer mikroporigen Schicht. Obwohl von Nickelelektrolyten zahlreiche Varianten bekannt sind, besteht weiterhin Bedarf nach verbesserten Nickelelektrolyten, die zu Beschichtungen führen, die veränderte oder verbesserte Korrosionseigenschaften haben. FIG. 4 shows a photograph of a microporous layer. Although numerous variants of nickel electrolytes are known, there is still a need for improved nickel electrolytes that result in coatings that have altered or improved corrosion properties.
US 3,471,271 beschreibt ein Verfahren, bei dem durch Zusatz großer Mengen von Feststoffen Risse in der Nickelschicht erzeugt werden. Aufgabe der vorliegenden Erfindung war es, Nickelelektrolyten bereitzustellen, mit denen Beschichtungen mit anderen, bevorzugt verbesserten Korrosionseigenschaften erhalten werden können. No. 3,471,271 describes a process in which cracks are produced in the nickel layer by adding large amounts of solids. The object of the present invention was to provide nickel electrolytes with which coatings with other, preferably improved, corrosion properties can be obtained.
Gelöst wird die Aufgabe durch einen Nickelelektrolyten enthaltend : The problem is solved by a nickel electrolyte containing:
- Nickelsalze  - nickel salts
- organische Säure - organic acid
- 0,05 bis 1 g/l anorganischen Feststoff mit einer Korngröße (d50) von 0,1 bis 3 μm.  - 0.05 to 1 g / l inorganic solid having a particle size (d50) of 0.1 to 3 microns.
Als Nickelverbindung eignen sich verschiedene Nickelsalze, insbesondere Nickelchlorid, Nickelacetat, Nickelsulfat sowie Mischungen davon. Die Menge des Nickels im Nickelektrolyten beträgt bevorzugt 5 bis 300 g/l, wobei eine Menge von 200 bis 280 g/l, jeweils berechnet auf NiCI, bevorzugt wird.. Suitable nickel compounds are various nickel salts, in particular nickel chloride, nickel acetate, nickel sulfate and mixtures thereof. The amount of nickel in the nickel electrolyte is preferably 5 to 300 g / L, with an amount of 200 to 280 g / L, each calculated to NiCl, being preferred.
Als organische Säure eigenen sich insbesondere niedermolekulare organische Säuren wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure und Mi- schungen hiervon. Geeignete Mengen der Säure betragen etwa 5 bis 150 g/l, bevorzugt 10 bis 30 g/l oder 40 bis 70 g/l. Particularly suitable organic acids are low molecular weight organic acids such as formic acid, acetic acid, propionic acid, butyric acid and about this. Suitable amounts of the acid are about 5 to 150 g / l, preferably 10 to 30 g / l or 40 to 70 g / l.
Weiterhin enthält der erfindungsgemäße Nickelelektrolyt einen anorganischen Feststoff, beispielsweise Aluminiumoxid, Siliziumdioxid, Silikate wie beispiels- weise Talkum, Siliziumcarbid oder Mischungen davon. Bevorzugte Gehalte des anorganischen Feststoffes liegen im Bereich von 0,1 bis 0,8 g/l, wobei eine Menge von 0,1 bis 0,3 g/l bevorzugt wird. Furthermore, the nickel electrolyte according to the invention contains an inorganic solid, for example aluminum oxide, silicon dioxide, silicates such as, for example, talc, silicon carbide or mixtures thereof. Preferred contents of the inorganic solid are in the range of 0.1 to 0.8 g / l, with an amount of 0.1 to 0.3 g / l being preferred.
Bevorzugt enthält der Nickelelektrolyt an Feststoff mehr als 0,1 g/l, beispielsweise 0,15 g/l oder 0,2 g/l. Bevorzugt enthält der Nickelelektrolyt weniger als 0,8 g/l oder weniger als 0,7 g/l, mehr bevorzugt weniger als 0,5 g/l und mehr bevorzugt weniger als 0,4 g/l oder weniger als 0,3 g/l. The nickel electrolyte preferably contains more than 0.1 g / l of solids, for example 0.15 g / l or 0.2 g / l. Preferably, the nickel electrolyte contains less than 0.8 g / L or less than 0.7 g / L, more preferably less than 0.5 g / L, and more preferably less than 0.4 g / L or less than 0.3 g / l.
In einzelnen Ausführungsformen kann die Menge an anorganischen Feststoffen auch 0,05 g/l bis 100 g/l oder 0,1 bis 60 g/l sein. Als mittlere Korngröße des anorganischen Feststoffes (d50) werden bevorzugt Korngrößen von 0,1 bis 3 μm mehr bevorzugt 0,8 bis 3 μm, noch mehr bevorzugt 1 bis 2,2 μm eingesetzt. In anderen Ausführungsformen kann die mittlere Korngröße im Bereich von 200 nm bis 5 μm oder 0,8 bis 3 μm liegen. In some embodiments, the amount of inorganic solids may also be 0.05 g / L to 100 g / L or 0.1 to 60 g / L. As average particle size of the inorganic solid (d50), preference is given to using particle sizes of from 0.1 to 3 μm, more preferably from 0.8 to 3 μm, even more preferably from 1 to 2.2 μm. In other embodiments, the mean grain size may be in the range of 200 nm to 5 μm or 0.8 to 3 μm.
Erfindungsgemäß wird durch den Elektrolyten erreicht, dass sich in der Schicht anorganische Partikel einlagern. Es entsteht eine mikrorissige Schicht, der eingelagerte anorganische Partikel enthält. Die entsprechenden erhaltenen Schichten sind dem Fachmann bisher nicht bekannt gewesen. According to the invention, it is achieved by the electrolyte that inorganic particles are incorporated in the layer. The result is a microcracked layer containing embedded inorganic particles. The corresponding layers obtained have hitherto not been known to the person skilled in the art.
Der Nickelelektrolyt kann übliche weitere Inhaltsstoffe von Elektrolyten enthalten, insbesondere Netzmittel, Puffersubstanzen und/oder Glanzbildner. In einer Ausführungsform enthält der Nickelelektrolyt zusätzlich Ammoniak. In einer Ausführungsform der Erfindung enthält der erfindungsgemäße Nickelelektrolyt keine Borsäure. Es wird bevorzugt, dass der Gehalt an Borsäure < 10 g/l, mehr bevorzugt < 5 g/l, noch mehr bevorzugt < 1 g/l ist. The nickel electrolyte may contain conventional further ingredients of electrolytes, in particular wetting agents, buffer substances and / or brighteners. In one embodiment, the nickel electrolyte additionally contains ammonia. In one embodiment of the invention, the nickel electrolyte according to the invention contains no boric acid. It is preferred that the content of boric acid is <10 g / L, more preferably <5 g / L, even more preferably <1 g / L.
Bevorzugt enthält der erfindungsgemäße Nickelektrolyt kein Reduktionsmittel wie Hypophosphit, wie es für außenstromlose Abscheidung eingesetzt wird. Bevorzugt liegt der Gehalt an Reduktionsmittel < 10 g/l, mehr bevorzugt < 5 g/l, noch mehr bevorzugt < 1 g/l. Preferably, the nickel electrolyte according to the invention contains no reducing agent such as hypophosphite, as it is used for electroless deposition. The content of reducing agent is preferably <10 g / l, more preferably <5 g / l, even more preferably <1 g / l.
Reduktionsmittel ist ein Mittel, dass aus dem Elektrolyten Ni2+ zu Ni reduzieren kann. Der erfindungsgemäße Nickelelektrolyt wird bevorzugt auf einen sauren pH- Wert zwischen pH 1,5 und 6,5, mehr bevorzugt 2 bis 5, und noch mehr bevorzugt 3 bis 4,5 eingestellt. Dies kann in üblicher Weise durch Zusatz von Säuren oder Laugen erfolgen. Reducing agent is a means that can reduce Ni 2+ from Ni to Ni. The nickel electrolyte according to the invention is preferably adjusted to an acidic pH between pH 1.5 and 6.5, more preferably 2 to 5, and even more preferably 3 to 4.5. This can be done in the usual way by adding acids or alkalis.
Gegenstand der Erfindung ist auch ein Verfahren zum Galvanisieren eines Bauteils umfassend den Schritt des Inkontaktbringens des Bauteils mit dem erfindungsgemäßen Nickelelektrolyten und Anlegen einer Stromdichte von 2 bis 15, bevorzugt 5 bis 10 A/dm2 bei einer Temperatur von 20 bis 55, vorzugsweise 25 bis 35°C. The invention also provides a process for electroplating a component comprising the step of contacting the component with the nickel electrolyte according to the invention and applying a current density of 2 to 15, preferably 5 to 10 A / dm 2 at a temperature of 20 to 55, preferably 25 to 35 ° C.
Erfindungsgemäß wird ein Nickelelektrolyt verwendet, der bereits ohne Zusatz von Feststoff zu einer mikrorissigen Struktur führt und zwar unabhängig davon, wie die weitere Behandlung des Elektrolyten durchgeführt wird, z.B. ob es sich bei der weiteren Behandlung der Schicht um ein Heiß- oder Kaltspülen handelt. Ein Nickelelektrolyt (ohne Zusatz eines Feststoffes) gilt im Sinne dieser Anmeldung als mikrorissiger Nickelelektrolyt, wenn bei Anlegen einer Stromdichte von 5 A/dm2 und einer Temperatur von 25 0C bei einer Schichtdicke von 2 μm gefolgt von einem Kaltspülen eine rissige Oberfläche erscheint. Es hat sich gezeigt, dass es für einen besonders guten Einbau einer größeren Anzahl an Feststoffpartikeln wichtig ist, dass die erzeugte Nickelschicht dicker ist als der d50-Wert der eingesetzten Partikel. Je dicker die Schichten sind, desto tiefer und fester scheint der Feststoff eingelagert worden zu sein. Schichtdicken von mehr als 2 μm bis zu 5 μm sind besonders bevorzugt. Die Chromschichtdicke zeigt weniger Einfluss. Chromschichtdicken im Bereich von etwa 0,375 bis 2 μm sind geeignet. According to the invention, a nickel electrolyte is used which already leads to a microcracked structure without the addition of solid, regardless of how the further treatment of the electrolyte is carried out, for example whether the further treatment of the layer involves hot or cold rinsing. A nickel electrolyte (without the addition of a solid), for the purposes of this application as micro cracking nickel electrolyte, when a cracked surface will appear upon application of a current density of 5 A / dm 2 and a temperature of 25 0 C at a coating thickness of 2 microns, followed by a cold rinse. It has been found that for a particularly good incorporation of a larger number of solid particles, it is important that the nickel layer produced is thicker than the d50 value of the particles used. The thicker the layers, the deeper and stronger the solid appears to have been incorporated. Layer thicknesses of more than 2 μm up to 5 μm are particularly preferred. The chrome layer thickness shows less influence. Chromium layer thicknesses in the range of about 0.375 to 2 microns are suitable.
Bei der Verfahrensdurchführung zeigt sich ein Einfluss der Bewegung des Bades. Eine geringe Bewegung des Bades scheint erforderlich zu sein, um die anorganischen Feststoffe in Nickelelektrolyten dispergiert zu halten. Eine zu große Bewegung scheint auf der anderen Seite schädlich zu sein, da vermutlich Partikel aus den Rissen herausgerissen werden, bevor sie hinreichend fest gebunden sind. In the process implementation shows an influence of the movement of the bath. A slight movement of the bath appears to be required to keep the inorganic solids dispersed in nickel electrolytes. Too much movement on the other hand seems to be detrimental, as it is believed that particles are ripped out of the cracks before they are sufficiently tightly bound.
Das Galvanisieren mit Nickelelektrolyten ist dem Fachmann grundsätzlich be- kannt und übliche Verfahrensmaßnahmen zum Galvanisieren mit Nickelelektrolyten sind auch für den neuen erfindungsgemäßen Elektrolyten anwendbar. Electroplating with nickel electrolytes is known in principle to a person skilled in the art and customary process measures for plating with nickel electrolytes are also applicable to the novel electrolyte according to the invention.
Durch den Einsatz des neuen Elektrolyten wird eine spezielle Struktur erhalten, die definierte Poren und Risse aufweist. Überraschenderweise führt dies zu einer deutlichen Veränderung der Korrosionseigenschaften. Typischerweise ist das Bauteil, das galvanisiert wird, aus Kunststoff oder Metall. In einem üblichen Verfahren werden ein oder mehrere Kupferschichten aufgebracht, die dann von ein oder mehrere Nickelschichten und abschließend von Dekorschichten, beispielsweise Chromschichten überzogen werden. Dabei ist mindestens eine der Nickelschichten eine erfindungsgemäße Nickelschicht. Der erfindungsgemäße Nickelelektrolyt kann vorteilhafterweise mit üblichen Anlagen der Galvanik aufgebracht werden, so dass keine baulichen Maßnahmen erforderlich sind. Gegenstand der Erfindung ist weiterhin ein Bauteil, das eine oder mehrere Schichten aufweist, die durch das erfindungsgemäße Verfahren erhältlich sind. By using the new electrolyte, a special structure is obtained which has defined pores and cracks. Surprisingly, this leads to a significant change in the corrosion properties. Typically, the component being electroplated is plastic or metal. In a conventional method, one or more copper layers are applied, which are then coated by one or more nickel layers and finally by decorative layers, for example chrome layers. At least one of the nickel layers is a nickel layer according to the invention. The nickel electrolyte according to the invention can advantageously be applied with conventional galvanic equipment, so that no structural measures are required. The invention furthermore relates to a component which has one or more layers obtainable by the process according to the invention.
Ein weiterer Gegenstand der Erfindung ist die Verwendung des erfindungsgemäßen Nickelelektrolyten zur Beschichtung von Bauteilen. Figur 1 zeigt die Ergebnisse eines CASS-Tests mit Bauteilen, die gemäß Vergleichsbeispiel 1 (hinten) bzw. Vergleichsbeispiel 2 (vorne) beschichtet wurden. Another object of the invention is the use of the nickel electrolyte according to the invention for coating components. Figure 1 shows the results of a CASS test with components coated according to Comparative Example 1 (back) and Comparative Example 2 (front).
Figur 2 zeigt Ergebnisses eines Tests gegen Calciumchloridsalze auf Basis von Kaolinpasten. Verglichen wurde ein Bauteil mit einer Beschichtung gemäß Beispiel 2 (oben) mit einer Beschichtung gemäß dem Vergleichsbeispiel 1 (unten). Figure 2 shows results of a test against calcium chloride salts based on kaolin pastes. A component with a coating according to Example 2 (top) with a coating according to Comparative Example 1 (bottom) was compared.
Figur 3 zeigt eine Aufnahme einer mikrorissigen Schicht des Standes der Technik. FIG. 3 shows a photograph of a microcracked layer of the prior art.
Figur 4 zeigt eine mikroporige Schicht gemäß dem Stand der Technik. Figur 5 zeigt eine Struktur, die mit dem erfindungsgemäßen Nickelelektrolyten erhalten wurde. Figure 4 shows a microporous layer according to the prior art. Figure 5 shows a structure obtained with the nickel electrolyte of the present invention.
Figur 6 zeigt eine Oberflächenaufnahme, die mit dem des erfindungsgemäßen Elektrolyten erhalten wurde, aber ohne Zusatz eines anorganischen Feststoffes. Figur 7 zeigt eine rasterelektronenmikroskopische Aufnahme ohne Feststoff der Oberfläche gemäß Figur 6. FIG. 6 shows a surface image obtained with that of the electrolyte according to the invention, but without the addition of an inorganic solid. FIG. 7 shows a scanning electron micrograph without solids of the surface according to FIG. 6.
Figur 8 eine rasterelektronenmikroskopische Aufnahme der erfindungsgemäßen Schichten mit einem eingebauten Feststoff. Figur 9 zeigt eine Beschichtung wie sie mit einem Elektrolyten der US 3,471,271 Beispiel 1 erhalten wurde (ohne Zusatz von Feststoff). 8 shows a scanning electron micrograph of the layers according to the invention with a built-in solid. FIG. 9 shows a coating as obtained with an electrolyte of US Pat. No. 3,471,271 Example 1 (without addition of solid).
Figur 10 zeigt unter identischen Bedingungen die Abscheidung eines erfindungsgemäßen Elektrolyten gemäß Beispiel 2 (ohne Zusatz von Feststoff). Überraschenderweise zeigt sich, dass die erfindungsgemäßen Schichten eine verbesserte Korrosionsbeständigkeit zeigen und zwar insbesondere bei der Korrosion von Calciumchlorid als Streusalz. Calciumchlorid hat einen niedrigeren Taupunkt als andere Salze und ist durch sein stark hyposkopisches Verhalten extrem aktiv. Die verbreiteten mikroporigen Chrombeschichtungen sind häufig bereits nach einem Winter deutlich sichtbar angegriffen. FIG. 10 shows, under identical conditions, the deposition of an electrolyte according to the invention according to Example 2 (without addition of solid). Surprisingly, it has been found that the layers according to the invention show improved corrosion resistance, in particular in the corrosion of calcium chloride as road salt. Calcium chloride has a lower dew point than other salts and is extremely active due to its strong hyposcopic behavior. The widespread microporous chromium coatings are often attacked clearly visible already after a winter.
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert. The invention is explained in more detail by the following examples.
Beispiel 1 (Vergleichsbeispiel) Example 1 (comparative example)
Nickelsulfat 240 g/l  Nickel sulphate 240 g / l
Nickelchlorid : 45 g/l  Nickel chloride: 45 g / l
Borsäure: 30 g/l  Boric acid: 30 g / l
Aluminiumoxid, d50 = 2,5 μm 0,3 g/l  Alumina, d50 = 2.5 μm 0.3 g / l
Glanzträger: 20 ml/l  Glossy carrier: 20 ml / l
Netz mitte I : 10 ml/l  Net middle I: 10 ml / l
Glanzzusatz: 0,5 ml/l  Brightening additive: 0.5 ml / l
Temperatur: 55°C  Temperature: 55 ° C
Stromdichte 4 A/dm2 Current density 4 A / dm 2
pH-Wert: 3,8 pH value: 3.8
Expositionszeit: 3 min  Exposure time: 3 min
Bewegung durch Lufteinblasung Die erzeugte Beschichtung zeigt eine feststoffabhängige mikroporige Oberfläche mit mindestens 8.000 Poren/cm2. Beispiel 2 Movement by air injection The coating produced shows a solids-dependent microporous surface with at least 8,000 pores / cm 2 . Example 2
Nickelchlorid : 250 g/l  Nickel chloride: 250 g / l
Ammoniumacetat: 30 g/l  Ammonium acetate: 30 g / l
Ammoniumchlorid : 20 g/l  Ammonium chloride: 20 g / l
Essigsäure: 15 ml/l  Acetic acid: 15 ml / l
Glanzzusatz: 1 ml/l  Brightening additive: 1 ml / l
Aluminiumoxid, d50 = 2μm : 0,5 g/l  Alumina, d50 = 2μm: 0.5g / l
Temperatur: 27°C  Temperature: 27 ° C
Stromdichte: 5 A/dm2 Current density: 5 A / dm 2
pH-Wert: 3,5 pH value: 3.5
Expositionszeit: 3 min  Exposure time: 3 min
Bewegung durch Lufteinblasung  Movement by air injection
Nach dem Heißspülprozess zeigt die Beschichtung eine definierte, zusammenhängende Strukturkombination mit vergrößerter Oberfläche und Mikroporen. After the hot flushing process, the coating shows a defined, coherent structure combination with increased surface area and micropores.
Beispiel 3 Example 3
Nickelchlorid : 180 g/l  Nickel chloride: 180 g / l
Ammoniumacetat: 30 g/l  Ammonium acetate: 30 g / l
Natriumchlorid : 50 g/l  Sodium chloride: 50 g / l
Essigsäure: 8 ml/l  Acetic acid: 8 ml / l
Propionsäure: 5 ml/l  Propionic acid: 5 ml / l
Glanzzusatz: 0,5 ml/l  Brightening additive: 0.5 ml / l
Talkum + Aluminiumoxid, d50 = 3 μm: 0,7 g/l  Talc + alumina, d50 = 3 μm: 0.7 g / l
Temperatur: 300C Temperature: 30 ° C
Stromdichte: 6 A/dm2 Current density: 6 A / dm 2
pH-Wert: 3,2 pH value: 3.2
Expositionszeit: 3 min  Exposure time: 3 min
Bewegung durch Lufteinblasung  Movement by air injection
Nach dem Heißspülprozess zeigt die Beschichtung eine definierte, zusammenhängende Strukturkombination mit vergrößerter Oberfläche und Mikroporen. Beispiel 4 After the hot flushing process, the coating shows a defined, coherent structure combination with increased surface area and micropores. Example 4
Nickelchlorid : 210 g/l  Nickel chloride: 210 g / l
Nickelsulfat: 44 g/l  Nickel sulfate: 44 g / l
Ammoniumacetat: 20 g/l  Ammonium acetate: 20 g / l
Ammoniumformiat: 10 g/l Ammonium formate: 10 g / l
Essigsäure: 10 ml/l  Acetic acid: 10 ml / l
Glanzzusatz: 1,0 ml/l  Brightening additive: 1.0 ml / l
Talkum + Siliziumdioxid, d50 = 1,5 μm 0,6 g/l Talc + silica, d50 = 1.5 μm 0.6 g / l
Temperatur: 29°C  Temperature: 29 ° C
Stromdichte: 5,5 A/dm2 Current density: 5.5 A / dm 2
pH-Wert: 3,5 pH value: 3.5
Expositionszeit: 3 min  Exposure time: 3 min
Bewegung durch Lufteinblasung Movement by air injection
Nach dem Heißspülprozess zeigt die Beschichtung eine definierte, zusammen- hängende Strukturkombination mit vergrößerter Oberfläche und Mikroporen. After the hot flushing process, the coating shows a defined, coherent structure combination with an enlarged surface area and micropores.
Beispiel 5 - CASS-Test Example 5 - CASS test
Der CASS-Test (copper accelerated acidic salt spray test) ist in DIN 50021 beschrieben. In einer Kammer werden Testteile mit einer Salzlösung mit folgender Zusammensetzung besprüht: - 50 g/l Natriumchlorid  The CASS test (copper accelerated acidic salt spray test) is described in DIN 50021. In a chamber test pieces are sprayed with a saline solution of the following composition: - 50 g / l sodium chloride
- 0,26 g/l Kupfer-(II)-Chlorid• 2 H2O - 0.26 g / l copper (II) chloride • 2 H 2 O.
- Essigsäure zur pH-Einstellung auf 3,1 bis 3,3  - Acetic acid for pH adjustment to 3.1 to 3.3
Nach 24, 48 oder 96 Stunden wird das Teil aus dem Nebel entnommen, gründlich gespült und abgetrocknet. Das gelöste Kupfersalz bewirkt dabei eine Auf- lösung des unedelsten Metalls im Schichtsystem. After 24, 48 or 96 hours, the part is removed from the mist, rinsed thoroughly and dried. The dissolved copper salt causes a dissolution of the least noble metal in the layer system.
Der CASS-Test zeigt den Korrosionsweg im Schichtsystem. Beispiel 6 - Ergebnisse der CASS-Tests The CASS test shows the corrosion path in the layer system. Example 6 - Results of the CASS Tests
Figur 1 zeigt die Ergebnisse des CASS-Tests nach 96 h. Bei dem hinteren Bauteil, beschichtet gemäß Vergleichsbeispiel 1, sind Korrosionserscheinungen zu erkennen, während das Bauteil mit einer Beschichtung gemäß Beispiel 2 (vor- ne) keine Korrosionserscheinungen zeigt.  Figure 1 shows the results of the CASS test after 96 h. In the case of the rear component, coated according to Comparative Example 1, corrosion phenomena can be seen, while the component with a coating according to Example 2 (front) shows no signs of corrosion.
Beispiel 7 - Calciumchloridkaolin-Test Example 7 - Calcium chloride kaolin test
Es wird eine Paste hergestellt aus 5 ml gesättigter Calciumchloridlösung und 3 g Kaolin und einem pH von 6,5 bis 7,5. Es handelt sich um eine breiartige Substanz. Eine definierte Menge wird auf einen Probenkörper in einem geeig- neten Durchmesser aufgebracht und bei 600C über 48 h gelagert. Dies ist ein beschleunigter Test zur Abschätzung der Beständigkeit gegenüber calciumchloridhaltigem Streusalz. A paste is prepared from 5 ml of saturated calcium chloride solution and 3 g of kaolin and a pH of 6.5 to 7.5. It is a mushy substance. A defined amount is applied to a sample body in a suitable diameter and stored at 60 0 C for 48 h. This is an accelerated test for assessing resistance to calcium chloride-containing road salt.
Beispiel 8 - Ergebnisse des Calciumchloridkaolin-Tests Example 8 - Results of the Calcium Chloride Kaolin Assay
Figur 2 zeigt, dass das gemäß Vergleichsbeispiel 1 beschichtete Bauteil (vor- ne) deutliche Korrosionsspuren zeigt, während das erfindungsgemäß beschichtete Teil (hinten) keine Anzeichen von Korrosion zeigt.  FIG. 2 shows that the component coated in accordance with Comparative Example 1 (front) shows marked traces of corrosion, while the part coated according to the invention (rear) shows no signs of corrosion.
Beispiel 9 Example 9
Ein Nickelelektrolyt, wie er im Beispiel 1 des US 3, 471, 271 beschrieben wird, wurde ohne Zusatz eines Feststoffes bei einer Stromstärke von 6 A/dm2 beschichtet. Figur 9 zeigt, dass die Struktur ohne Zusatz von Feststoff keine Risse aufweist. A nickel electrolyte as described in Example 1 of US 3, 471, 271, was coated without the addition of a solid at a current of 6 A / dm 2. FIG. 9 shows that the structure has no cracks without addition of solid.
Unter identischen Beschichtungsbedingungen wurde der Elektrolyt gemäß Beispiel 2 beschichtet. Figur 10 zeigt, dass dieser Elektrolyt ohne Zusatz von Feststoffen bereits rissige Strukturen ergibt. Under identical coating conditions, the electrolyte was coated according to Example 2. FIG. 10 shows that this electrolyte already gives cracked structures without the addition of solids.

Claims

Patentansprüche claims
1. Nickelelektrolyt enthaltend : 1. Nickel electrolyte containing:
- Nickelsalze,  Nickel salts,
- organische Säure oder deren Salze,  - organic acid or its salts,
- 0,05 bis 1 g/l anorganischen Feststoff mit einer Korngröße (d50) von - 0.05 to 1 g / l of inorganic solid with a particle size (d50) of
0,1 bis 3 μm. 0.1 to 3 μm.
2. Nickelektrolyt nach Anspruch 1, dadurch gekennzeichnet, dass der Gehalt an Nickel 5 bis 300 g/l, bevorzugt 200 bis 280 g/l bezogen auf NiCI beträgt. 2. nickel electrolyte according to claim 1, characterized in that the content of nickel is 5 to 300 g / l, preferably 200 to 280 g / l based on NiCl.
3. Nickelektrolyt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die organische Säure ausgewählt wird aus Ameisensäure, Essigsäure, Propionsäure, Buttersäure und deren Salzen und Mischungen davon und/oder dass die organische Säure in einer Menge von 5 bis 150 g/l, bevorzugt 10 bis 30 g/l oder 40 bis 70 g/l enthalten ist. 3. nickel electrolyte according to claim 1 or 2, characterized in that the organic acid is selected from formic acid, acetic acid, propionic acid, butyric acid and their salts and mixtures thereof and / or that the organic acid in an amount of 5 to 150 g / l, preferably 10 to 30 g / l or 40 to 70 g / l is contained.
4. Nickelelektrolyt nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass der Nickelelektrolyt ohne Zusatz von anorganischen Feststoffen schichten bildet, die mikrorissig sind. 4. nickel electrolyte according to claim 1 to 3, characterized in that the nickel electrolyte without the addition of inorganic solids forms layers that are microcracked.
5. Nickelektrolyt nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der anorganische Feststoff ausgewählt aus Alumi- niumoxid, Siliziumdioxid, Silikaten wie Talkum, Siliziumcarbid und Mischungen davon. 5. nickel electrolyte according to at least one of claims 1 to 4, characterized in that the inorganic solid selected from alumina niumoxid, silica, silicates such as talc, silicon carbide and mixtures thereof.
6. Nickelektrolyt nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Gehalt an anorganischem Feststoff 0,1 g/l bis 0,3 g/l beträgt. 6. nickel electrolyte according to at least one of claims 1 to 5, characterized in that the content of inorganic solid is 0.1 g / l to 0.3 g / l.
7. Nickelektrolyt nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die mittlere Korngröße des anorganischen Feststoffes (d50) bei 0,8 bis 3 μm, bevorzugt 0,1 μm bis 2,2 μm liegt. 7. nickel electrolyte according to at least one of claims 1 to 6, characterized in that the average particle size of the inorganic solid (d50) is 0.8 to 3 .mu.m, preferably 0.1 .mu.m to 2.2 .mu.m.
8. Nickelektrolyt nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass eine oder mehrere der Inhaltsstoffe Netzmittel, Puffersubstanzen, Glanzbildner, Ammoniak, Alkali-, Erdalkaliverbindung, Ammoniumverbindungen enthalten sind. 8. nickel electrolyte according to at least one of claims 1 to 7, characterized in that one or more of the ingredients wetting agents, buffer substances, brighteners, ammonia, alkali, alkaline earth metal compound, ammonium compounds are included.
9. Nickelektrolyt nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Nickel in Form von Nickelchlorid, Nickelsulfat, Nickelacetat oder Mischungen davon eingebracht wird. 9. nickel electrolyte according to at least one of claims 1 to 8, characterized in that the nickel is introduced in the form of nickel chloride, nickel sulfate, nickel acetate or mixtures thereof.
10. Nickelelektrolyt nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass der pH-Wert 1,5 bis 6,5, bevorzugt 3 bis 4,5 be- trägt. 10. Nickel electrolyte according to at least one of claims 1 to 9, characterized in that the pH is 1.5 to 6.5, preferably 3 to 4.5.
11. Nickelelektrolyt nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass kein Reduktionsmittel und/oder keine Borsäure und/oder kein EDTA enthalten ist. 11. nickel electrolyte according to at least one of claims 1 to 10, characterized in that no reducing agent and / or no boric acid and / or no EDTA is included.
12. Verfahren zum Galvanisieren eines Bauteils umfassend den Schritt des Inkontaktbringens des Bauteils mit einem Nickelelektrolyten gemäß einem der Ansprüche 1 bis 11 und Anlegen einer Stromdichte von 2 bis 15, bevorzugt 5 bis 10 A/dm2 bei einer Temperatur von 20 bis 55, vorzugsweise 25 bis 35°C. 12. A method of galvanizing a component comprising the step of contacting the component with a nickel electrolyte according to any one of claims 1 to 11 and applying a current density of 2 to 15, preferably 5 to 10 A / dm 2 at a temperature of 20 to 55, preferably 25 to 35 ° C.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass auf das Bau- teil eine oder mehrere Kupferschichten und gegebenenfalls weitere Nickelschichten aufgebracht werden und abschließend eine oder mehrere Deckschichten, Chromschichten aufgebracht werden und gegebenenfalls ein Heißspülprozess bei mindestens 500C durchgeführt wird. 13. The method according to claim 12, characterized in that on the component one or more copper layers and optionally further nickel layers are applied and finally one or more cover layers, chrome layers are applied and optionally a Heißspülprozess at least 50 0 C is performed.
14. Bauteil umfassend eine oder mehrere Schichten, wobei mindestens eine Schicht, die durch das Verfahren gemäß Anspruch 12 erhältlich ist und anorganische Feststoffe enthält. 14. A component comprising one or more layers, wherein at least one layer obtainable by the method according to claim 12 and containing inorganic solids.
15. Verwendung eines Nickelelektrolyten nach einem der Ansprüche 1 bis 11 zur Beschichtung von Bauteilen. 15. Use of a nickel electrolyte according to one of claims 1 to 11 for coating components.
EP10742444.2A 2009-07-07 2010-07-07 Nickel electrolyte Not-in-force EP2451997B1 (en)

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US5217536A (en) * 1990-06-06 1993-06-08 C. Uyemura & Co., Ltd. Composite plating apparatus
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